One-pack type thermally crosslinkable polymer composition

Abstract

A one-pack type thermally crosslinkable polymer composition comprising a thermoplastic polymer having a carboxylic acid group or an acid anhydride group, and a polyamine compound as a latent curing agent, which is suitably used as an adhesive to adhere a skin material to a substrate of an automobile interior parts.

Description

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a one-pack type thermally crosslinkable polymer composition. In particular, the present invention relates to a one-pack type thermally crosslinkable polymer composition comprising a specific thermoplastic polymer and a polyamine compound as a latent curing agent, which composition is useful as an adhesive for adhering a substrate layer and a skin material of an interior part for automobiles, in particular, as an adhesive for precoating a skin material.

[0003] 2. Prior Art

[0004] As interior parts of automobiles, laminates comprising substrate layers and skin materials laminated on the substrate layers have been used to improve quality. Such a laminate is produced by a vacuum molding or press molding method in which an adhesive is applied to either one or both of the substrate layer and the skin material, and the molding and adhering are performed at the same time.

[0005] In such a molding method, a solvent-base adhesive is generally used, which comprises a polyesterpolyurethane containing a polyester as a polyol component dissolved in a solvent. However, this type of an adhesive has insufficient heat resistance required for the use in automobile interior applications, and a two-pack type adhesive containing a polyisocyanate as a curing agent is practically used. Such a two-pack type adhesive has some drawbacks such that it causes the environmental pollution since the adhesive is spray coated in a parts-molding line, and that the working time for mixing, coating and molding/adhering is restricted since two liquid components are reacted on mixing and cured.

SUMMARY OF THE INVENTION

[0006] An object of the present invention is to provide a one-pack type thermally crosslinkable polymer composition which can solve the above drawbacks of the conventional adhesives, and which is useful, for example, as an adhesive for precoating a skin material in the production of an interior part of an automobile.

[0007] Accordingly, the present invention provides a one-pack type thermally crosslinkable polymer composition comprising a thermoplastic polymer having a carboxylic acid group or an acid anhydride group, and a polyamine compound as a latent curing agent.

[0008] The one-pack type adhesive of the present invention can be stored at room temperature without the occurrence of a reaction, and crosslinked at a temperature of 60° C. or higher to exert good adhesion strength with good heat resistance. In addition, the polymer composition can avoid the use of any solvent in the production of a laminate having a skin material, when it is precoated on the skin material.

DETAILED DESCRIPTION OF THE INVENTION

[0009] The thermoplastic polymers having a carboxylic acid group or an acid anhydride group may be olefinic polymers, butadiene polymers, ester polymers, carbonate polymers, urethane polymers, amide polymers, etc., all of which have a carboxylic acid group or an acid anhydride group. In particular, olefinic polymers having a carboxylic acid group or an acid anhydride group is preferable from the viewpoint of adhesion properties to polyolefins.

[0010] Typical examples of such thermoplastic polymers include polypropylene (PP), styrene-ethylene/butene-styrene copolymers (SEBS), ethylene-vinyl acetate copolymers (EVA), ethylene-acrylate copolymers (EEA), and the like, each of which is modified by the introduction of a dibasic unsaturated acid (e.g. maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.) or its anhydride. Such modified polymers are known and commercially available.

[0011] Hereinafter, thermoplastic polymers having a carboxylic acid group or an acid anhydride group will be referred to as “COOH-modified polymers”.

[0012] Polyamine compounds used as latent curing agents are divided into the following two classes (I) and (II):

[0013] (I) Solid polyamine compounds having a melting point of 60° C. or higher, preferably 80 to 200° C., for example, aromatic polyamines such as 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminobiphenyl, 2,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, etc.; aliphatic polyamines such as 1,12-dodecanediamine, 1,10-decanediamine, 1,8-octanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, etc.; hydrazide base polyamine such as 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin of the formula: 1

[0014] (melting point: 121-123° C.), (the compound of the formula: NH2NHCO—(CH2)18—CONHNH2 (melting point: 174-181° C.), the compound of the formula: NH2NHCO—(CH2)6—CH═CH—(CH2)2—CH═CH—(CH2)6—CONHNH2 (melting point: 147-155° C.); and the like. These polyamines may be used singly or in admixture of two or more.

[0015] An amount of the polyamine to be used is at least an equivalent amount to the carboxyl groups of the COOH-modified polymer. When the amount of the polyamine is less than the equivalent amount, the crosslinking of the polymer is insufficient, and the heat resistance of the cured material deteriorates. When the amount of the polyamine is too large, the curing agent is liberated, so that adherents may be insufficiently adhered. Accordingly, a preferred amount of the polyamine to be used is one to 10 times the equivalent amount.

[0016] (II) Hydrolyzable reaction products obtained by the reaction of diamines having two amino or imino groups in a molecule, and carbonyl compounds (aldehydes or ketones)

[0017] Examples of such diamines include aliphatic diamines (e.g. dimethylaminopropylamine, diethylaminopropylamine, monomethylaminopropylamine, methyliminobispropylamine, hexamethylenediamine, 1,10-diaminododecane, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, di-β-aminoethylsulfide, di-β-aminoethyldisulfide, di-β-aminoethylether, di-γ-amino-n-propylether, triglycoldiamine, N,N-dibutyltrimethylhexamethylenediamine, etc.); alicyclic diamines (e.g. 1,8-p-menhanediamine, isophoronediamine, diaminocyclohexane, 4,4′-methylenebis(cyclohexylamine), 1,3-bisaminomethylcyclohexane, 3-aminomethyl-3,3,5-trimethylcyclohexylamine, N,N′-butylisophoronediamine, N-aminoethylpiperazine, 3-(3-aminopropyl)-3,2-dimethylpiperazine, etc.); aromatic or aromatic aliphatic diamines (e.g. xylylenediamine, diaminodiphenylether, phenylenediamine, triamionxylene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylether, etc.); and the like. In particular, aliphatic diamines having 8 or more carbon atoms are preferred.

[0018] The above carbonyl compound is generally represented by the formula:

R1—CO—R2

[0019] wherein R1 and R2 are the same or different and represent a hydrogen atom, a lower alkyl group having 1 to 8 carbon atom, preferably 1 to 6 carbon atoms (e.g. a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert.-butyl group, etc.), a phenyl group or a naphthyl group, or R1 and R2 together form a cyclic hydrocarbon group (e.g. a cyclohexyl group or a cyclopentyl group, etc.), provided that R1 and R2 are not hydrogen atoms or naphthyl groups at the same time.

[0020] Specific examples of the carbonyl compound include aliphatic aldehydes (e.g. acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, diethylacetoaldehyde, etc.), aromatic aldehydes (e.g. benzaldehyde, etc.), cyclic ketones (e.g. cyclopentanone, trimethylcyclopentanone, cyclohexanone, trimethylcyclohexanone, etc.), aliphaticketones (e.g. acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, etc.); and the like.

[0021] The diamine and the carbonyl compound may be reacted under conventional conditions. For example, the diamine and an equivalent or excessive amount of the carbonyl compound in relation to the diamine are reacted in a suitable solvent (e.g. toluene, xylene benzene, etc.), optionally in the presence of a water absorbent (e.g. molecular sieves, anhydrous magnesium sulfate, etc.) at room temperature or an elevated temperature while removing water. Thus, a hydrolyzable reaction product is obtained. Here, a reaction product obtained using an aldehyde as a carbonyl compound is referred to as “aldimine”, while one obtained using a ketone as a carbonyl compound is referred to as “ketimine”.

[0022] Ketimines are usually less stable and more easily hydrolyzed than aldimines. That is, aldimines having a relatively low molecular weight have good storage stability, while ketimines having a low molecular weight are unstable. Thus, solid diamines having a relatively high molecular weight and good stability (low activity) are preferably used to prepare ketimines. More preferably, a reaction medium, which functions also as a carbonyl compound, is used, since the reaction is always in an equilibrium state.

[0023] An amount of the aldimine or the ketimine may be at least an equivalent amount to the carboxyl groups of the above COOH-modified polymer. When the amount of the aldimine or the ketimine is less than the equivalent amount, the degree of crosslinking is insufficient, and thus the cured material of the composition has low heat resistance. When the amount of the aldimine or the ketimine is too excessive, the adhesion of the adherents with the composition may be insufficient. Accordingly, a preferred amount of the polyamine to be used is one to 10 times the equivalent amount.

[0024] The one-pack type thermally crosslinkable polymer composition of the present invention preferably comprises the COOH-modified polymer, the solid polyamine (I) or the aldimine or ketimine (II), which are dispersed in the above specific ratio in a suitable organic solvent (e.g. toluene, xylene, benzene, 1,1,1-trichloroethane, methylene chloride, etc.). If desired, the one-pack type thermally crosslinkable polymer composition of the present invention may optionally contain a conventional thermoplastic resin (e.g. acrylic resin, vinyl resin, polyamide resin, polyester resin, polyolefin, polyurethane, SEBS, etc.), tackifiers, polyolefin-base tackifiers, dyes, pigments, etc.

[0025] The one-pack type thermally crosslinkable polymer composition of the present invention having the above composition can be used as an adhesive, a coating material, an adhesive sheet, a film or sheet-form adhesive, a paint, and the like. In particular, the one-pack type thermally crosslinkable polymer composition of the present invention is useful as an adhesive which is used in the production of laminates for automobile interior parts, which comprise a substrate layer (e.g. ABS boards, polyphenylene oxide (NORYL®) boards, ASG boards, polycarbonate boards, polypropylene boards, wood composite boards, steel plates, etc.) and skin materials (e.g. polyvinyl chloride foams, polyolefin foams such as polyethylene foams, polypropylene foams, etc.).

[0026] The production steps of such laminates will be explained in detail.

[0027] i) Firstly, the polymer composition of the present invention is precoated in a thickness of 5 to 500 μm uniformly on the surface of a skin material, and dried at a temperature of room temperature to 100° C. The dry thickness of the composition is from 20 to 300 μm.

[0028] Alternatively, the polymer composition of the present invention may be discontinuously coated on the surface of a skin material. For example, the polymer composition may be coated in a linear (or bead) form or a dot form. In the case of discontinuous coating, the amount of the polymer composition can be reduced to about half to two thirds of the amount in the case of the overall area coating. The polymer composition may be discontinuously applied with a multi-nozzle, or transferred with a roll or a doctor knife coater.

[0029] By the above application methods, an adhesive layer having no blocking properties is formed on the skin material. The precoated skin material may be supplied to a following molding process as such, or it may be stored for a certain time, for example, several months at a temperature of room temperature to 100° C. and then supplied to the molding process. Even when the precoated skin material is stored for a long time, it can exert a sufficient adhesion force.

[0030] When a latent curing agent in the adhesive layer of the precoated skin material is the aldimine or the ketimine, it tends to be easily hydrolyzed with moisture (or water) in an air to form a free amine and to cause the hydrolysis. Thus, the precoated skin material should be stored in a dry state in a sealed container during the storage or in the period prior to molding in a subsequent step.

[0031] ii) Then, the precoated skin material produced in the step i) is laminated on a substrate heated at a specific temperature (usually around 80° C.) while optionally heating the skin material at a certain temperature (usually from 100 to 160° C.), if desired, and heat pressed under a pressure of 0.1 kg/cm2 or more for at least 10 seconds to effect the molding and adhering at the same time. Thus, a laminate having good heat resistant adhesion properties. In addition, such a molding process can prevent environmental pollution caused by the evaporation of solvents.

[0032] Such laminates can be used as automobile interior parts such as inside trims (e.g. door trims, front pillars, deck side trims, center pillars, etc.), instrument panels, molded ceilings, console boxes, and the like.

[0033] In the above, the polymer composition of the present invention is explained in connection with its application as a precoating adhesive of skin materials, although it can be advantageously used as a thermally crosslinkable adhesive film, sheet or tape having a thickness of 50 to 500 μm by forming, that is, coating and drying, the composition on a suitable support such as a release paper. In such a case, the properties of the film may be adjusted by the addition of the above-described thermoplastic resins.

EXAMPLES

[0034] The present invention will be explained further in detail by following Examples, which do not limit the scope of the invention.

Examples 1-3 and Comparative Examples 1 and 2

[0035] 1) Preparation of Adhesive

[0036] A COOH-modified polymer, a thermoplastic resin, a tackifier and a solid polyamine compound shown in Table 1 were added to and dispersed in a mixed solvent of toluene and cyclohexane (volume ratio of 1:1) by mixing at 60° C. for 2 hours to obtain an adhesive.

[0037] With the prepared adhesive, the blocking tendency was evaluated as follows. The result is shown in Table 1.

[0038] Blocking Tendency

[0039] The adhesive was coated on a skin layer of a polypropylene foam (PPF) laminated with a thermoplastic polypropylene layer (TPO), and dried. Then, a pair of dried precoated skin materials (TPO/PPF/Adhesive) were laminated with facing the adhesive layer of one skin material with the TPO of the other and kept standing at 60° C. for 72 hours while applying a load of 0.5 kg/cm2. Immediately thereafter, the upper skin material was lifted up, and the blocking state was observed, and ranked as follows:

[0040] O: The skin materials were not blocked, and the lower skin material was not lifted up together.

[0041] X: The skin materials were blocked, and the skin materials were lifted up together.

[0042] 2) Production of Laminated Molded Article and Evaluation of Adhesion

[0043] The adhesive prepared in the above step 1) was coated in a thickness of 500 μm on a polyethylene foam skin material having a thickness of 3 mm, and dried at 60° C. for 5 minutes to obtain a precoated skin material.

[0044] Then, the precoated skin material was heated to a temperature of 120 to 130° C. with a far infrared heater and laminated on a polypropylene board which had been heated at 80° C. for 2 minutes, followed by compressing under a load of 0.5 kg/cm2 for 20 seconds to obtain a laminated molded article.

[0045] With the produced laminated molded article, an initial creep, an initial peel strength and heat resistant creep were measured under the following conditions

[0046] Initial Creep

[0047] Immediately after the production of the molded article, a load of 200 g/25 mm was applied in the 90 degree angle direction in an atmosphere of 60° C. After 5 minutes, the peeled length (mm) was measured.

[0048] Initial Peel Strength

[0049] A peel strength was measured after 5 minutes from the completion of the lamination.

[0050] Heat Resistant Creep

[0051] After keeping the laminated molded article at 20° C. for 24 hours, a load of 200 g/25 mm was applied in the 90 degree angle direction in an atmosphere of 90° C. After 24 hours, the peeled length (mm) was measured.

[0052] The results are shown in Table 1, in which “CF” stands for cohesive failure, and “MB” stand for the breakage of the skin material. In Comparative Example 2, the composition was gelled in the course of the preparation. Thus, no test was carried out.

	TABLE 1
	Example No.	C. Ex. No.
	1	2	3	1	2
Maleic anhydride-modified PP1)	100	—	—	100	100
Maleic anhydride-modified SEBS2)	—	100	—	—	—
COOH-modified PB3)	—	—	100	—	—
SEBS4)	20	20	20	20	20
Tackifier5)	100	100	100	100	100
Hydrazide-base polyamine6)	30	30	30	—	—
Hexamethylene diamine	—	—	—	—	15
(melting point: 39-42° C.)
Mixed solvent	700	700	700	700	700
Blocking tendency	O	O	O	X	—
Initial creep (mm)	3	4	4	30	—
	CF	CF	CF	CF
Initial peel strength (kg/25 mm)	2.3	2.2	2.2	2.3	—
	MB	MB	MB	MB
Heat resistant creep (mm)	0	0	0	Fall	—
Notes:
1)MTPP (trade name) manufactured by TOYO KASEI Co., Ltd.
2)TOUGHTECK (trademark) M-1953 manufactured by Asahi Chemical Industry Co., Ltd.
3)M-2000-80 (trade name) manufactured by NIPPON PETROCHEMICAL CO., LTD.
4)TOUGHTECK (trademark) H-1042 manufactured by Asahi Chemical Industry Co., Ltd.
5)NEOPOLYMER 140 manufactured by NIPPON PETROCHEMICAL CO., LTD.
6)1,3-Bis(hydrazinocarboethyl)-5-isopropylhydantoin (melting point: 120-123° C.)

Example 4

[0053] A laminated molded article was prepared in the same manner as in Example 1 except that the polymer composition was coated on a polyethylene foam skin material as follows:

[0054] Overall Coating:

[0055] The polymer composition was spray coated on the skin material of a polypropylene foam to a thickness of 650 g/m2 (dry thickness of 100 μm), and dried at 60° C. for 5 minutes to obtain a precoated skin material.

[0056] Bead Coating:

[0057] 1. The polymer composition was coated in the form of a bead having a diameter of about 2 mm in an amount of a half of the coated amount in the case of the 100 μm dry thickness.

[0058] 2. The polymer composition was coated in the form of a bead having a diameter of about 4 mm in an amount of two thirds of the coated amount in the case of the 100 μm dry thickness.

[0059] Dot Coating:

[0060] 1. The polymer composition was coated in the form of a square having a side of 4 mm in an amount of a half of the coated amount in the case of the 100 μm dry thickness.

[0061] 2. The polymer composition was coated in the form of a square having a side of 8 mm in an amount of two thirds of the coated amount in the case of the 100 μm dry thickness.

[0062] Then, the initial creep, initial peel strength and heat resistant creep were measured in the same manner as in Example 1. The results are shown in Table 2.

	TABLE 2
	Bead coating
	Overall	(lateral)1)	Dot coating
	coating	1/2	1/3	1/2	2/3
Initial creep	2	2	4	10	2
(mm)	CF	CF	CF	CF	CF
Initial peel strength	5.1	4.7	5.5	4.5	6.7
(kg/25 mm)	MB	MB	MB	MB	MB
Heat resistant creep	0	1.3	4	Fall	0
(mm)
Note:
1)“Bead coating (lateral)” means that the creep was in the direction perpendicular to the coating direction of beads.

[0063] An amount of the coated polymer composition can be decreased while keeping the good adhesion properties when it is discontinuously coated.

Examples 5 and 6

[0064] 1) Preparation of Adhesive

[0065] The components shown in Table 3 were mixed and dispersed in the same manner as in Example 1 to obtain an adhesive.

[0066] The aldimine and the ketimine used in these Examples were prepared as follows:

[0067] Preparation of Aldimine

[0068] In a reactor vessel replaced with nitrogen gas, hexamethylenediamine (50 wt. parts), a water-absorbent (molecular sieve) (90 wt. parts) and absolute toluene (50 wt. parts) were charged. Then, benzaldehyde (100 wt. parts) was gradually added to the stirred mixture and reacted while cooling at 10° C.

[0069] Preparation of Ketimine

[0070] In a reactor vessel replaced with nitrogen gas, 1,10-diaminododecane (50 wt. parts), acetone (100 wt. parts) and a water-absorbent (molecular sieve) (70 wt. parts) were charged at once and reacted.

[0071] 2) Production of Laminated Molded Article and Evaluation of Adhesion

[0072] An adhesive was coated in the thickness of 500 μm on the skin layer of PPF laminated with TPO, which was used in the above evaluation of the blocking tendency, and dried at 60° C. for 5 minutes to obtain a precoated skin material. Then, the precoated skin material was kept in a sealed container.

[0073] The precoated skin material was taken out of the container one day before the use, and maintained at room temperature to effect the hydrolysis of the adhesive. Then, the precoated skin material was laminated on a polypropylene board, which had been heated at 80° C. for 2 minutes, under a load of 0.5 kg/cm2 for 20 seconds while heating the skin material at 120 to 130° C. to obtain a laminate. The results of the same adhesion property tests as those in Examples 1-3 are shown in Table 3.

	TABLE 3
	Example No.
	5	6
	Maleic anhydride-modified PP	100	100
	SEBS	20	20
	Tackifier	100	100
	Aldimine	30	—
	Ketimine	—	30
	Mixed solvent	700	700
	Blocking tendency	0	0
	Initial creep (mm)	2	2
		CF	CF
	Initial peel strength (kg/25 mm)	2.2	2.3
		MB	MB
	Heat resistant creep (mm)	0	0

[0074] From the above results, the polymer compositions of the present invention prepared in Examples 1 to 6 have good initial adhesion strength, and heat resistant adhesion strength.

Claims

1. A one-pack type thermally crosslinkable polymer composition comprising a thermoplastic polymer having a carboxylic acid group or an acid anhydride group, and a polyamine compound as a latent curing agent.

2. The one-pack type thermally crosslinkable polymer composition according to claim 1, wherein said thermoplastic polymer having a carboxylic acid group or an acid anhydride group is an olefinic polymer having a carboxylic acid group or an acid anhydride group.

3. The one-pack type thermally crosslinkable polymer composition according to claim 1, wherein said thermoplastic polymer having a carboxylic acid group or an acid anhydride group is polypropylene or a styrene-ethylene/butene-styrene copolymer, which is modified with maleic anhydride.

4. The one-pack type thermally crosslinkable polymer composition according to claim 1, wherein said polyamine compound is a solid polyamine compound having a melting point of at least 60° C.

5. The one-pack type thermally crosslinkable polymer composition according to claim 4, wherein said solid polyamine compound is a hydrazine-base polyamine.

6. The one-pack type thermally crosslinkable polymer composition according to claim 4 or 5, wherein said solid polyamine compound has a melting point of 80 to 200° C.

7. The one-pack type thermally crosslinkable polymer composition according to claim 5, wherein said hydrazine-base polyamine is 1,3-bis(hydrazinocarboethyl)-5-isopropyl-hydantoin having a melting point of 120 to 123° C.

8. The one-pack type thermally crosslinkable polymer composition according to claim 1, wherein said polyamine compound is a hydrolyzable reaction product obtained by the reaction of a diamine having two amino or imino groups in a molecule, and a carbonyl compound selected from the group consisting of aldehydes and ketones.

9. The one-pack type thermally crosslinkable polymer composition according to claim 8, wherein said hydrolyzable reaction product is a reaction product obtained by the reaction of an aliphatic diamine and an aromatic aldehyde.

10. The one-pack type thermally crosslinkable polymer composition according to claim 8, wherein said hydrolyzable reaction product is a reaction product obtained by the reaction of an aliphatic diamine having at least 8 carbon atoms and an aliphatic ketone.

11. The one-pack type thermally crosslinkable polymer composition according to claim 1, which is used as an adhesive for precoating an adherent.

12. The one-pack type thermally crosslinkable polymer composition according to claim 1, which is discontinuouly applied to a surface of an adherent.

13. The one-pack type thermally crosslinkable polymer composition according to claim 12, which is applied in the linear form or a dot form.

14. The one-pack type thermally crosslinkable polymer composition according to claim 13, wherein the applied amount of said composition is half to two thirds of an amount in the case of overall area coating.

15. A precoated skin material comprising a skin material for an automobile interior part, and the one-pack type thermally crosslinkable polymer composition according to claim 1 which is coated on the surface of said skin material.

16. The precoated skin material according to claim 15, wherein said composition is discontinuously coated on the surface of said skin material.

17. The precoated skin material according to claim 16, wherein said composition is coated on the surface of said skin material in the linear form or a dot form.

18. The precoated skin material according to claim 16, wherein the applied amount of said composition is half to two thirds of an amount in the case of overall area coating.

19. A thermally crosslinkable adhesive film produced by forming the one-pack type thermally crosslinkable polymer composition according to claim 1.

20. The thermally crosslinkable adhesive film according to claim 19, wherein said one-pack type thermally crosslinkable polymer composition further comprises a thermoplastic resin.

21. A laminated molded article for an automobile interior part, comprising a substrate layer, and the precoated skin material according to claim 12 which is adhered to said substrate layer by vacuum molding or press molding.