JP7112298B2 - Surface material for laminates and vehicle interior materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate and a skin material for vehicle interior materials using the laminate.

For example, as an upholstery covering the surface of a vehicle seat cushion, there is a laminate in which a covering layer is adhered to one surface of a foamed polyurethane layer, and a surface layer is adhered to the other surface of the laminate. The upholstery material is cut and sewn into a shape to cover the seat cushion.

The covering layer is provided for the purpose of improving the slipperiness in order to improve the work of sewing and the work of covering the seat cushion with the upholstery material, protecting the back surface of the polyurethane foam layer, and the like.
On the other hand, the surface layer is made of an appropriate material such as genuine leather, synthetic leather, fabric, or the like, depending on the decorativeness and feel required of the vehicle seat.

In addition, since heat resistance is required for the skin material that covers the surface of the seat cushion of a vehicle, there is a case where a polyurethane reactive hot-melt adhesive is used for bonding the foamed polyurethane layer, the cover layer, and the surface layer (Patent Document 1). ). A polyurethane reactive hot-melt adhesive is mainly composed of a polyurethane prepolymer obtained by reacting a polyester polyol and a polyisocyanate.

JP 2017-136735 A

However, the upholstery covering the surface of the seat cushion of a vehicle is required to contain a small amount of VOCs (volatile organic compounds) that adversely affect the human body. In addition, the amount of VOC in the skin material that covers the surface of the seat cushion of a vehicle varies depending on the material of the surface layer, and even if the same type of genuine leather is used, the amount of VOC varies depending on the part where it is used. .

The present invention has been made in view of the above points. It is an object of the present invention to reduce the amount of VOCs in a skin material of a vehicle interior material to which a surface layer made of a predetermined material is adhered.
Furthermore, since the skin material of the vehicle interior material is required to have flame retardancy in consideration of the case of vehicle fire, the present invention provides a low VOC and flame retardant laminate and a vehicle interior material. The purpose is to provide a skin material.

The invention of claim 1 provides a laminate comprising a polyurethane foam layer obtained from a polyurethane foam resin composition containing a polyol, a polyisocyanate, a foaming agent, a catalyst and a flame retardant, and a coating layer laminated on the polyurethane foam resin composition. The product contains tin ricinoleate containing an active hydrogen group as the catalyst and a phosphorus-containing solid flame retardant as the flame retardant, and the foamed polyurethane layer and the coating layer comprise a polyol component (A) and a polyisocyanate (B ) as a raw material, and the polyurethane prepolymer in the polyurethane hot melt adhesive contains an aliphatic dicarboxylic acid having 10 to 12 carbon atoms as the polyol component (A) A crystalline polyester polyol (a-1) formed by condensation reaction of an acid and an aliphatic diol having 4 to 6 carbon atoms and a polyether polyol (a-2) are included, and the polyether in the polyol component (A) The content of the polyol (a-2) is 30 to 80 parts by mass per 100 parts by mass of the polyol component (A).

The invention of claim 2 is the invention according to claim 1, wherein the flame retardant in the foamed polyurethane resin composition includes the phosphorus-containing solid flame retardant and melamine powder having an average particle size of 0.1 to 0.5 μm. characterized by

The invention of Claim 3 is characterized in that, in Claim 1 or 2, the phosphorus-containing solid flame retardant in the foamed polyurethane resin composition is a phosphate ester compound.

The invention of claim 4 is the invention according to any one of claims 1 to 3, wherein the crystalline polyester polyol (a-1) of the polyurethane prepolymer in the hot melt adhesive has a number average molecular weight of 1,000 to 5,000. and the polyether polyol (a-2) is characterized by having a number average molecular weight of 1,000 to 4,000.

The invention of claim 5 is the hot melt adhesive according to any one of claims 1 to 4, wherein the polyol component (A) of the polyurethane prepolymer in the hot melt adhesive is an amorphous one or more polyols selected from the group consisting of polypolyester polyols, polycarbonate polyols, and low-molecular-weight diols having a number average molecular weight of 500 or less.

The invention of claim 6 is the polyurethane foam layer according to any one of claims 1 to 5, wherein a surface layer is adhered to a surface of the polyurethane foam layer opposite to the covering layer with the polyurethane hot-melt adhesive. Characterized by

According to a seventh aspect of the invention, there is provided a skin material for vehicle interior materials, which is obtained by using the laminate described in the sixth aspect.

ADVANTAGE OF THE INVENTION According to this invention, the surface material of the laminated body and interior material for vehicles with low VOC and flame retardancy is obtained.

It is a sectional view showing a layered product of one embodiment of the present invention. FIG. 4 is a cross-sectional view showing a laminate according to another embodiment of the invention; 1 is a table showing configurations, combustibility, VOC, etc. of examples of the present invention and comparative examples.

A laminate 10 according to one embodiment of the present invention shown in FIG.
The foamed polyurethane layer 11 is obtained by foaming a foamed polyurethane resin composition containing a polyol, a polyisocyanate, a foaming agent, a catalyst and a flame retardant.
Polyether polyols or polyester polyols are used as polyols. Examples of polyether polyols include compounds obtained by addition polymerization of alkylene oxides to polyhydric alcohols, as well as polypropylene glycol and polytetramethylene glycol. Glycerin, dipropylene glycol, trimethylolpropane and the like are used as polyhydric alcohols. Ethylene oxide, propylene oxide and the like are used as the alkylene oxide.

Examples of polyether polyols include triols obtained by addition polymerization of propylene oxide to glycerin, triols obtained by addition polymerization of ethylene oxide thereto, diols obtained by addition polymerization of propylene oxide to dipropylene glycol, and the like.

The polyether polyol may be a polyether ester polyol obtained by reacting a polyoxyalkylene polyol with a polycarboxylic anhydride and a compound having a cyclic ether group. Examples of polyoxyalkylene polyols include polyethylene glycol, polypropylene glycol, propylene oxide adducts of glycerin, and the like. Examples of polycarboxylic acid anhydrides include anhydrides such as succinic acid, adipic acid and phthalic acid. Examples of compounds having a cyclic ether group (alkylene oxides) include ethylene oxide and propylene oxide. Polyether polyols are preferable to polyester polyols because they are highly reactive with polyisocyanates and are not hydrolyzed.

Polyester polyols include condensation polyester polyols obtained by reacting polycarboxylic acids such as adipic acid and phthalic acid with polyols such as ethylene glycol, propylene glycol and glycerin, as well as lactone polyester polyols and polycarbonate polyester polyols. is used.

As the polyisocyanate, aliphatic or aromatic polyisocyanates having two or more isocyanate groups, mixtures thereof, modified polyisocyanates obtained by modifying them, and the like can be used. For example, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, hydrogenated MDI, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone Diisocyanates, xylylene diisocyanate (XDI) hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, and modifications thereof derivatives, and the like. Other prepolymers can also be used. The polyisocyanate may be used alone or in combination of two or more.

The isocyanate index is preferably 80-100. If the isocyanate index is less than 80, it is difficult to obtain the foamed polyurethane layer 11 with good mechanical properties such as tensile strength and elongation, while if it exceeds 100, the flexibility of the foamed polyurethane layer 11 is reduced. The isocyanate index (INDEX) is a value obtained by multiplying the number of moles of isocyanate groups per 1 mole of active hydrogen groups contained in the urethane raw material by 100, [(isocyanate equivalent in polyurethane foam resin composition/polyurethane foam resin composition equivalent of active hydrogen in the substance) × 100].

As blowing agents, water, CFC alternatives, or hydrocarbons such as pentane can be used alone or in combination. In the case of water, carbon dioxide gas is generated during the reaction between polyol and polyisocyanate, and the carbon dioxide gas causes foaming. The amount of water as a foaming agent is preferably about 2 to 5 parts by mass with respect to 100 parts by mass of polyol. Moreover, when other foaming agents are used together with water, the amount of the other foaming agents is appropriately determined.

As the catalyst, tin ricinoleate containing an active hydrogen group is preferred, and it is more preferred to use it in combination with an amine catalyst. By including tin ricinoleate in the catalyst, the amount of VOC in the foamed polyurethane layer 11 and laminate 10 can be reduced. Amine catalysts include triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, tetramethylguanidine and the like.

A phosphorus-containing solid flame retardant is used as the flame retardant. The phosphorus-containing solid flame retardant is a compound with low volatility, and both non-halogen and halogen-containing compounds can be used, and a phosphate ester compound is used. Specifically, triphenyl phosphate (white, flaky), aromatic condensed phosphate (white powder to granular), tris(tribromoneopentyl) phosphate (white, crystalline, powder), etc. are used. be able to. The content of the phosphorus-containing solid flame retardant is preferably 3 to 15 parts by mass per 100 parts by mass of the polyol. If the content is less than 3 parts by mass, the low combustibility of the foamed polyurethane layer 11 cannot be sufficiently improved. On the other hand, if it exceeds 15 parts by mass, there is a tendency that the foaming balance is lost and it becomes difficult to obtain a good foamed polyurethane layer 11 .

In addition to the phosphorus-containing solid flame retardant used in the present invention, the phosphorus-containing flame retardant includes a phosphorus-containing liquid flame retardant. However, since the phosphorus-containing liquid flame retardant has higher volatility than the phosphorus-containing solid flame retardant, the polyurethane foam layer 11 and the laminate 10 contain more VOCs.

For the flame retardant of the present invention, it is preferable to use melamine resin powder together with the phosphorus-containing solid flame retardant. Melamine [C ₃ N ₃ (NH ₂ ) ₃ ] does not contain oxygen, so it can suppress the progress of combustion. The average particle size of the melamine powder is preferably 0.1-0.5 μm. Fine melamine powder with an average particle diameter of 0.1 to 0.5 μm is dispersed in the polyurethane foam layer 11, and melts to form a film when the polyurethane foam layer 11 is burned, blocking oxygen and suppressing combustion. guessed. If the average particle size of the melamine powder is less than 0.1 μm, the production of the melamine powder becomes complicated and the production cost increases. On the other hand, if it exceeds 0.5 μm, the dispersibility of the melamine powder in the foamed polyurethane layer 11 is lowered, and the effect of improving the low combustibility cannot be sufficiently achieved.

The content of melamine powder is preferably 3 to 13 parts by weight per 100 parts by weight of polyol. If the content is less than 3 parts by mass, the effect of promoting low combustibility of the foamed polyurethane layer 11 cannot be achieved sufficiently. On the other hand, if it exceeds 13 parts by mass, the balance of foaming tends to be lost, and there is a possibility that a good foamed polyurethane layer 11 cannot be obtained.

The density and thickness of the foamed polyurethane layer 11 are appropriately determined, but when the laminate 10 is used as a skin material for a vehicle interior material such as a vehicle seat cushion, it should be bent along the surface of the vehicle interior material. For example, it is preferable to have a density of 20 to 35 kg/m ³ and a thickness of 3 to 10 mm.

The polyurethane foam resin composition preferably contains other additives such as a foam stabilizer. Examples of foam stabilizers include silicone compounds, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium laurate, polyether siloxanes, and phenolic compounds. The content of the foam stabilizer is exemplified as 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the polyol.
Further examples of other additives include known additives such as fillers, stabilizers, colorants, plasticizers and antibacterial agents, if necessary.

The foamed polyurethane layer 11 is manufactured by a known polyurethane foam manufacturing method. Mold foaming and slab foaming are known methods for producing polyurethane foams. Mold foaming is a method in which a foaming polyurethane resin composition is filled in a mold and foamed in the mold. On the other hand, slab foaming is a method in which a foamed polyurethane resin composition is mixed, discharged onto a belt conveyor, and foamed at room temperature under atmospheric pressure. As the foamed polyurethane layer of the present invention, a slab foam obtained by cutting polyurethane foam produced by slab foaming into a predetermined thickness is more preferable.

As the coating layer 15, a nonwoven fabric, a woven fabric, or a knitted fabric is preferable. In particular, tricot among knitted fabrics has elasticity and stretchability, so when it is used as the covering layer 15, when the laminate 11 is used as the skin material of the vehicle interior material, it deforms along the surface of the vehicle interior material. It is easy to do, and wrinkles are less likely to occur in the skin material. Moreover, the material of the coating layer 15 includes nylon, polyester, and the like.

The foamed polyurethane layer 11 and the coating layer 15 are adhered by a polyurethane hot-melt adhesive 13 containing a polyurethane prepolymer made from polyol component (A) and polyisocyanate (B). The polyurethane prepolymer is obtained by reacting the polyol component (A) and the polyisocyanate (B) as raw materials with the polyol component (A) in a stoichiometrically excessive amount. It is a polyurethane prepolymer with isocyanate groups (NCO).

The polyol component (A) comprises a crystalline polyester polyol (a-1) obtained by condensation reaction of an aliphatic dicarboxylic acid having 10 to 12 carbon atoms and an aliphatic diol having 4 to 6 carbon atoms; ) and are included.

The content of the crystalline polyester polyol (a-1) in the polyol component (A) is preferably 10 to 60 parts by mass, more preferably 20 to 40 parts by mass, per 100 parts by mass of the polyol component. be. By setting it as such a range, it becomes possible to maintain a favorable solidification time and high peel strength (adhesive strength).

The content of the polyether polyol (a-2) in the polyol component (A) is preferably 30 to 80 parts by mass, and 40 to 60 parts by mass with respect to 100 parts by mass of the polyol component (A). is more preferable. Such a range enables high flexibility and good peel strength (adhesive strength).

The content ratio of the crystalline polyester polyol (a-1) and the polyether polyol (a-2) is preferably 20:80 to 70:30, more preferably 30:70 to 50:50. be.

The crystalline polyester polyol (a-1) is a polyol obtained by a condensation reaction of an aliphatic dicarboxylic acid having 10 to 12 carbon atoms and an aliphatic diol having 4 to 6 carbon atoms. Specifically, aliphatic dicarboxylic acids include decanedioic acid (sebacic acid, C10), undecanedioic acid (C11) and dodecanedioic acid (C12). On the other hand, aliphatic diols having 4 to 6 carbon atoms include butanediol (eg, 1,3-butanediol, 1,4-butanediol, etc.), pentanediol (eg, 1,5-pentanediol, etc.) and hexanediol. (eg, 1,6-hexanediol) and the like.

"Crystalline polyester polyol" indicates a melting point of 30° C. or higher, while "amorphous polyester polyol" indicates a melting point of 30° C. or lower or absent. Such crystallinity can be adjusted by appropriately selecting the acid/glycol component. Using a differential scanning calorimeter, the melting peak in the range of −80° C.→100° C. under a temperature program of 25° C.→−80° C.→100° C. (heating rate 5° C./min) is defined as the melting point.

The crystalline polyester polyol (a-1) preferably has a number average molecular weight within the range of 1,000 to 5,000, more preferably within the range of 2,000 to 4,500.

Examples of the polyether polyol (a-2) include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc. obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, respectively, and copolyethers thereof. be done. The polyether polyol (a-2) can also be obtained by polymerizing the above cyclic ether using a polyhydric alcohol such as glycerin or trimethylolethane.

The polyether polyol (a-2) preferably has a number average molecular weight in the range of 1,000 to 4,000, more preferably in the range of 1,500 to 3,000.

The polyol component (A) further contains one or more polyols selected from the group consisting of amorphous polyester polyols, polycarbonate polyols and low molecular weight diols having a molecular weight of 500 or less as other polyols (a-3). is preferred.

Amorphous polyester polyols include, for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; Cyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, or their acid esters or acid anhydrides with ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, polyester polyol obtained by dehydration condensation reaction with 1,9-nonanediol or a mixture thereof; polylactone diol obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone; .

Examples of polycarbonate polyols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Diol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, at least one polyhydric alcohol such as an alicyclic dihydroxy compound, and diethylene Examples thereof include those obtained by reacting with carbonate, dimethyl carbonate, diethyl carbonate and the like.

The low molecular weight diol is not particularly limited as long as it has a number average molecular weight of 500 or less. For example, ethylene glycol, propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl -1,3-hexanediol.

Other polyols (a-3) may be used alone or in combination of two or more. In addition, other polyols (a-3) may include polyols other than those described above. The content of the other polyol (a-3) in the polyol component (A) is preferably 30 parts by mass or less per 100 parts by mass of the polyol component (A). By setting it in such a range, it is possible to improve wet heat aging resistance, peel strength (adhesive strength), and the like. The lower limit of the content of the other polyol (a-3) in the polyol component (A) is not particularly limited.

Examples of the polyisocyanate (B) include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, hydrogenated MDI, 1,5-naphthalene diisocyanate, 1,6- Hexamethylene diisocyanate (HDI), isophorone diisocyanate, xylylene diisocyanate (XDI) hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI) 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane Examples include triisocyanate, and modified products and derivatives thereof. Polyisocyanate (B) may be used alone or in combination of two or more.

The NCO group content of the polyurethane prepolymer having terminal isocyanate groups is not particularly limited, but is preferably 1.0 to 2.5%. The NCO group content is a value measured according to JIS K1603-1.

The content of the polyurethane prepolymer is preferably 70-100% by mass, more preferably 80-100% by mass, with respect to the entire polyurethane hot-melt adhesive 13 .

The polyurethane hot-melt adhesive 13 may contain other components as additives together with the polyurethane prepolymer. Examples of additives to be blended include oil components (plasticizers), tackifying resins, antioxidants, waxes, heat stabilizers, fillers, catalysts, and the like. These additives may be used alone or in combination of two or more.

Examples of oil components include paraffinic oils, naphthenic oils, and aromatic oils. A vegetable oil or the like may be used as the oil component.

Tackifying resins include aliphatic petroleum resins, aromatic petroleum resins, hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, terpene resins, styrene resins, rosin resins and modified resins thereof. One or more tackifying resins selected from the group consisting of can be exemplified.

Examples of antioxidants include phenolic antioxidants (e.g., Irganox 1010 (manufactured by BASF)), sulfur-based antioxidants (e.g., SUMILIZER TP-D (manufactured by Sumitomo Chemical Co., Ltd.)) and phosphorus-based antioxidants (e.g., , Irgafos 168 (manufactured by BASF), and JP-650 (manufactured by Johoku Kagaku).

Waxes include natural waxes {e.g., animal waxes (beeswax, spermaceti, etc.), plant waxes (Japan wax, etc.), petroleum waxes (paraffin wax, etc.), etc.} and synthetic waxes {e.g., synthetic hydrocarbons ( low-molecular-weight polyethylene, etc.), fatty acid esters (polyethylene glycol, etc.), etc.} can be exemplified.

Examples of catalysts include metal-based catalysts and amine catalysts. The catalyst may be used alone or in combination of two or more.

The polyurethane hot-melt adhesive 13 can be produced by a known polyurethane hot-melt adhesive production method. For example, (1) a predetermined amount of polyisocyanate (B) is added dropwise to a reaction vessel containing a predetermined amount of polyol component (A) and then heated to convert the isocyanate groups of polyisocyanate (B) into polyol component (A). A polyurethane prepolymer is prepared by reacting under conditions in which there is an excess to the hydroxyl groups of (2) A method of producing a polyurethane hot-melt adhesive by dropping a predetermined amount of optionally blended additives into a polyurethane prepolymer and stirring the mixture. The reaction between the isocyanate of the polyisocyanate (B) and the hydroxyl group of the polyol component (A) is carried out at a temperature of, for example, 50-120°C, preferably 60-100°C. The reaction time is, for example, 1 to 15 hours.

Laminate 10 is manufactured by applying a predetermined amount of polyurethane hot-melt adhesive 13 to either or both of one side of polyurethane foam layer 11 and coating layer 15, and then bonding one side of polyurethane foam layer 11 and coating layer 15 together. The polyurethane hot-melt adhesive 13 is cooled and hardened in this state.

The method of applying the polyurethane hot-melt adhesive 13 may be a non-contact method such as spray coating or a contact method such as roll coater coating. The coating amount of the polyurethane hot-melt adhesive 13 is preferably 5-50 g/m ² , more preferably 10-30 g/m ² . As conditions for the non-contact method, a pressure of 0.01 to 0.4 MPa and a temperature of 100 to 160° C. are exemplified.

After cooling and curing, the polyurethane hot-melt adhesive 13 exhibits higher adhesive strength by reacting uncured terminal isocyanate in the polyurethane prepolymer with moisture in the air to form a crosslinked structure.

In another embodiment of the laminate 20 shown in FIG. 2, the covering layer 15 is laminated on one surface of the polyurethane foam layer 11, and the surface layer 19 is laminated on the surface of the polyurethane foam layer 11 opposite to the covering layer 15. consists of the The covering layer 15 and the foamed polyurethane layer 11 are adhered with a polyurethane hot-melt adhesive 13 , and the surface layer 19 and the foamed polyurethane layer 11 are adhered with a polyurethane hot-melt adhesive 17 . Polyurethane hot melt adhesives 13 and 17 are the same as hot melt adhesive 13 described for laminate 10 in FIG.

The surface layer 19 is made of an appropriate material such as natural leather, synthetic leather, fabric (plastic film lined product), or the like.

Laminate 20 is manufactured in the same manner as laminate 10 in FIG. A predetermined amount of polyurethane hot-melt adhesive 17 is applied to either one or both of the layers 19, then the surface of the foamed polyurethane layer 11 and the surface layer 19 are overlapped, and in this state, the polyurethane hot-melt adhesive 19 is cooled and hardened. It can be done by After cooling and curing, the polyurethane hot-melt adhesive 19 exhibits higher adhesive strength by reacting uncured terminal isocyanate in the polyurethane prepolymer with moisture in the air to form a crosslinked structure. Alternatively, the surface layer 19 may be first adhered to one side of the polyurethane foam layer 11 with the polyurethane hot-melt adhesive 17, and then the covering layer 15 may be adhered to the opposite side of the polyurethane foam layer 11 with the polyurethane hot-melt adhesive 13. good.

The laminate 20 is suitable as an upholstery material for vehicle interior materials such as vehicle seat cushions, headrests, and instrument panels. A vehicle interior material is mainly composed of a cushioning material made of foamed polyurethane or the like, and the surface of the cushioning material is covered with a skin material. When the laminate 20 is used as an upholstery material for an interior material for a vehicle, a plurality of laminate pieces obtained by cutting the laminate 20 to a predetermined size are sewn together with the surface layer 19 on the front side to form a vehicle. Make it a shape that covers the interior material for the car.

Using the following raw materials, a foamed polyurethane resin composition having the formulation of each example and each comparative example shown in FIG. 3 was prepared, slab foamed, and then cut into a thickness of 5 mm. Foamed polyurethane layers of Comparative Examples 1 to 6 were produced. In addition, the numerical value of the raw material in the foaming polyurethane resin composition column of FIG. 3 is a mass part.

Polyol: polyether polyol, functional group number 3, molecular weight 3000, hydroxyl value 56 mgKOH/g, product name; GP3050NS, manufactured by Sanyo Chemical Industries, Ltd. Flame retardant 1: melamine powder, average particle size 0.3 μm, product name; melamine, Mitsui Chemicals Co., Ltd. flame retardant 2: phosphorus-containing solid flame retardant, aliphatic phosphate amidate, product name; -880, manufactured by Daihachi Chemical Industry Co., Ltd. Foaming agent: water Foam stabilizer: silicone-based foam stabilizer, product name; B-8244, manufactured by Evonik Amine catalyst: N,N-dimethylaminohexanol, product name; 25, manufactured by Kao Corporation Metal catalyst 1: Tin ricinoleate containing an active hydrogen group, product name; KOSMOS EF, manufactured by Evonik Metal catalyst 2: Stannous octylate, manufactured by Johoku Chemical Industry Co., Ltd.

Density (apparent density, compliant with JIS K 7222), tensile strength (compliant with JIS K 6700-5 3), and elongation (compliant with JIS K 6400-5 3) were measured for the foamed polyurethane layer of each example and each comparative example. .

In addition, a coating layer was adhered to one side of the foamed polyurethane layer of Examples 1 to 3 and Comparative Examples 1 to 4 with a hot melt adhesive 1, and Examples 1 to 3 and Comparative Examples 1 to 4 were used. A laminate of Example 4 was produced. The coating layer was Nylon Tricot 15d, manufactured by Kiryu Tricot Co., Ltd., and was coated with Hot Melt Adhesive 1 at a coating amount of 20 g/m ² by spraying.

Hot melt adhesive 1 is prepared by putting the following polyol component (A) into a reaction vessel, adding polyisocyanate and an amine catalyst, and reacting at 100° C. for 3 to 4 hours to obtain NCO%=2.0%. A hot melt adhesive 1 was prepared from a polyurethane prepolymer of

(Hot melt adhesive 1)
- Polyol component (A)
Crystalline polyester polyol (a-1): sebacic acid / butanediol, melting point 60 ° C., number average molecular weight 4000, 35 parts by mass Polyether polyol (a-2): polypropylene glycol (addition form PO alone), number average molecular weight 2000 , 50 parts by mass Other polyol (a-3): amorphous polyester polyol, phthalic acid / neopentyl glycol, number average molecular weight 1000, 15 parts by mass Polyisocyanate (B)
Diphenylmethane diisocyanate, NCO% = 33%, 24 parts by mass Amine catalyst: N,N-dimethyldodecylamine, 0.05 parts by mass

As for the foamed polyurethane layer of Example 4, a coating layer was adhered to one side thereof with the hot-melt adhesive 2 to produce a laminate of Example 4. The coating layer was nylon tricot 15d manufactured by Kiryu Tricot Co., Ltd., and was coated with hot melt adhesive 2 at a coating amount of 20 g/m ² by spraying.

Hot-melt adhesive 2 is prepared by putting the following polyol component (A) into a reaction vessel, adding polyisocyanate and an amine catalyst, and reacting at 100° C. for 3 to 4 hours to obtain NCO%=2.0%. A hot melt adhesive 2 was prepared from a polyurethane prepolymer of

(Hot melt adhesive 2)
- Polyol component (A)
Crystalline polyester polyol (a-1): dodecanedioic acid / hexanediol, melting point 70 ° C., number average molecular weight 4000, 35 parts by mass Polyether polyol (a-2): polypropylene glycol (addition form PO alone), number average molecular weight 2000, 50 parts by mass Other polyol (a-3): Polycarbonate diol (addition type PO alone), melting point 50 ° C., number average molecular weight 1000, 15 parts by mass Polyisocyanate (B)
Diphenylmethane diisocyanate, NCO% = 33%, 24 parts by mass Amine catalyst: N,N-dimethyldodecylamine, 0.05 parts by mass

As for the foamed polyurethane layer of Example 5, a coating layer was adhered to one side thereof with the hot-melt adhesive 3 to produce a laminate of Example 5. The coating layer was nylon tricot 15d manufactured by Kiryu Tricot Co., Ltd., and was coated with hot melt adhesive 3 at a coating amount of 20 g/m ² by spraying.

Hot-melt adhesive 3 is prepared by putting the following polyol component (A) into a reaction vessel, adding polyisocyanate and an amine catalyst, and reacting at 100° C. for 3 to 4 hours to obtain NCO%=2.0%. A hot melt adhesive 3 was prepared from a polyurethane prepolymer of

(Hot melt adhesive 3)
- Polyol component (A)
Crystalline polyester polyol (a-1): dodecanedioic acid / hexanediol, melting point 70 ° C., number average molecular weight 4000, 35 parts by mass Polyether polyol (a-2): polypropylene glycol (addition form PO alone), number average molecular weight 2000, 50 parts by mass Other polyol (a-3): butyl ethyl propanediol (addition type PO alone), melting point 43 ° C., 15 parts by mass Polyisocyanate (B)
Diphenylmethane diisocyanate, NCO% = 33%, 40 parts by mass Amine catalyst: N,N-dimethyldodecylamine, 0.05 parts by mass

As for the foamed polyurethane layer of Example 6, a coating layer was adhered to one side thereof with the hot-melt adhesive 4 to produce a laminate of Example 6. The coating layer was Nylon Tricot 15d, manufactured by Kiryu Tricot Co., Ltd., and was coated with a hot melt adhesive 4 at a coating amount of 20 g/m ² by spraying.

Hot-melt adhesive 4 is prepared by putting the following polyol component (A) into a reaction vessel, adding polyisocyanate and an amine catalyst, and reacting at 100° C. for 3 to 4 hours to obtain NCO%=2.0%. A polyurethane prepolymer was produced and designated as a hot melt adhesive 6.

(Hot melt adhesive 4)
- Polyol component (A)
Crystalline polyester polyol (a-1): sebacic acid / hexanediol, melting point 65 ° C., number average molecular weight 4000, 20 parts by mass Polyether polyol (a-2): polypropylene glycol (addition form PO alone), number average molecular weight 2000 , 80 parts by mass Polyisocyanate (B)
Diphenylmethane diisocyanate, NCO% = 33%, 18 parts by mass Amine catalyst: N,N-dimethyldodecylamine, 0.05 parts by mass

For the foamed polyurethane layer of Comparative Example 5, a covering layer (nylon tricot 15d, manufactured by Kiryu Tricot Co., Ltd.) was adhered by frame lamination to produce a laminate of Comparative Example 5.

For the foamed polyurethane layer of Comparative Example 6, the covering layer was adhered with the hot melt adhesive 5 to produce a laminate of Comparative Example 6. The coating layer was nylon tricot 15d manufactured by Kiryu Tricot Co., Ltd., and was coated with hot melt adhesive 5 at a coating amount of 20 g/m ² by spraying.

The hot-melt adhesive 5 is a polyol component of crystalline polyester polyol (adipic acid/butanediol), melting point 58°C, number average molecular weight 2000, 30 parts by mass, and polypropylene glycol, number average molecular weight 1000, 70 parts by mass. Put into a container, add 20 parts by mass of diphenylmethane diisocyanate, NCO% = 33%, and 0.05 parts by mass of an amine catalyst (N,N-dimethyldodecylamine) as a polyisocyanate, and add 3 to 3 parts by mass at 100 ° C. A polyurethane prepolymer having an NCO% of 2.0% was produced by reacting for 4 hours, which was designated as Hot Melt Adhesive 5.

Combustibility, VOC value, FOG value and TVOC value were measured for the laminates of Examples 1 to 6 and Comparative Examples 1 to 6.
Flammability measurements were made based on FMVSS302. Judgment of combustibility is "self-extinguishing" if the flame disappears within 51 mm of the burning distance and within 60 seconds. min or less is "acceptable", and the flame retardancy increases in the order of "acceptable" → "self-extinguishing" → "noncombustible", and "noncombustible" is the most excellent in flame retardancy.

The VOC value was measured by preparing a 7 mg test piece (with a coating layer) from the laminates of Examples 1 to 6 and Comparative Examples 1 to 6, placing the test piece in a glass tube, and using a thermal desorption device (product name : TDSA (including KAS, KAS-3+, KAS-4); manufactured by Gestel) was used to measure the VOCs specified in "German Automobile Manufacturers Association VDA278". Specifically, each test piece is heated at a temperature of 90 ° C. for 30 minutes, and the gas generated during the heating is measured by a gas chromatograph mass spectrometer (product name: gas chromatograph mass spectrometer (product number: 6890-5973N) ; manufactured by Agilent), and the VOC value was calculated. Further, in accordance with the provisions of "German Automobile Manufacturers Association VDA278", following the VOC value measurement, the sample is heated at a temperature of 120°C for 1 hour, and the gas generated during the heating is similarly analyzed with a gas chromatograph mass spectrometer. The FOG value was also calculated together. FOG is a phenomenon in which a volatilized substance adheres to glass and becomes cloudy white.

The TVOC value is the total emission of volatile organic compounds and was measured according to PV-3341. Specifically, heating is performed at a temperature of 120° C. for 5 hours, and the gas generated during the heating is analyzed with a gas chromatograph, and the peak area is calculated.
Moreover, VOC etc. were evaluated. The evaluation criteria were "O" when all of VOC < 100 ppm, FOG < 250 ppm, and TVOC < 30 µgC/g were satisfied, and "X" when none of them were satisfied.

Also, the laminates of Examples 1 to 6 and the laminates of Comparative Examples 1 to 6 were comprehensively evaluated. The criteria for the comprehensive evaluation are: if the combustibility judgment is non-combustible and the evaluation of VOC, etc. is “○”, the comprehensive evaluation is “〇”; It was set as evaluation "x".
Note that "-" in the FOG and TVOC result columns in FIG. 3 means unmeasured.

(Example 1)
The foamed polyurethane layer of Example 1 contains 100 parts by mass of polyol, 5 parts by mass of flame retardant 2 (phosphorus-containing solid flame retardant), 3.9 parts by mass of foaming agent (water), 1.1 parts by mass of foam stabilizer, and an amine catalyst. It was obtained from a foamed polyurethane resin composition comprising 0.18 parts by mass, 0.8 parts by mass of metal catalyst 1 (tin ricinoleate containing an active hydrogen group), and an isocyanate index of 103. The foamed polyurethane layer of Example 1 has a density of 25.0 kg/m ³ , a tensile strength of 97 kPa, and an elongation of 198%.

In the laminate of Example 1, a coating layer was adhered to one side of the foamed polyurethane layer with the hot melt adhesive 1, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 79 ppm, and the FOG value was 30 ppm. . The laminate of Example 1 has good flame retardancy and low VOC.

(Example 2)
The foamed polyurethane layer of Example 2 contains 100 parts by weight of polyol, 4 parts by weight of flame retardant 1 (melamine powder), 4 parts by weight of flame retardant 2 (phosphorus-containing solid flame retardant), 3.95 parts by weight of foaming agent (water), 1.1 parts by mass of a foam stabilizer, 0.18 parts by mass of an amine catalyst, 1.3 parts by mass of metal catalyst 1 (tin ricinoleate containing an active hydrogen group), and an isocyanate index of 103. It is. The foamed polyurethane layer of Example 2 has a density of 25.7 kg/m ³ , a tensile strength of 90 kPa and an elongation of 216%.

In the laminate of Example 2, a coating layer was adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 1, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 74 ppm, the FOG value was 42 ppm, It has a TVOC value of 15 μgC/g, an evaluation of VOC and the like of “◯”, and an overall evaluation of “◯”. The laminate of Example 2 has good flame retardancy and low VOC.
(Example 3)
The foamed polyurethane layer of Example 3 contains 100 parts by weight of polyol, 4 parts by weight of flame retardant 1 (melamine powder), 4 parts by weight of flame retardant 2 (phosphorus-containing solid flame retardant), 3 parts by weight of foaming agent (water), and foam stabilizer. 1.5 parts by mass of an agent, 0.1 parts by mass of an amine catalyst, 2.75 parts by mass of metal catalyst 1 (tin ricinoleate containing an active hydrogen group), and an isocyanate index of 110. be. The foamed polyurethane layer of Example 3 has a density of 34.9 kg/m ³ , a tensile strength of 132 kPa and an elongation of 204%.

In the laminate of Example 3, a coating layer was adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 1, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 86 ppm, the FOG value was 59 ppm, It has a TVOC value of 3 μgC/g, an evaluation of VOC and the like of “◯”, and an overall evaluation of “◯”. The laminate of Example 3 has good flame retardancy and low VOC.

(Example 4)
The foamed polyurethane layer of Example 4 was obtained from the same foamed polyurethane resin composition as that of Example 2, and had the same physical properties as those of the foamed polyurethane layer of Example 2.
In the laminate of Example 4, a coating layer was adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 2, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 70 ppm, the FOG value was 34 ppm, The TVOC value was 14 μgC/g, the evaluation of VOC and the like was “◯”, and the overall evaluation was “◯”. The laminate of Example 4 has good flame retardancy and low VOC.

(Example 5)
The foamed polyurethane layer of Example 5 was obtained from the same foamed polyurethane resin composition as that of Example 2, and had the same physical properties as those of the foamed polyurethane layer of Example 2.
In the laminate of Example 5, a coating layer was adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 3, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 69 ppm, the FOG value was 41 ppm, It has a TVOC value of 8 μgC/g, an evaluation of VOC and the like of “◯”, and an overall evaluation of “◯”. The laminate of Example 5 has good flame retardancy and low VOC.

(Example 6)
The foamed polyurethane layer of Example 6 was obtained from the same foamed polyurethane resin composition as that of Example 2, and had the same physical properties as those of the foamed polyurethane layer of Example 2.
In the laminate of Example 6, a coating layer was adhered to one side of the foamed polyurethane layer with a hot-melt adhesive 4, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 88 ppm, the FOG value was 53 ppm, The TVOC value was 10 μgC/g, the evaluation of VOC, etc. was “◯”, and the overall evaluation was “◯”. The laminate of Example 6 has good flame retardancy and low VOC.

(Comparative example 1)
The foamed polyurethane layer of Comparative Example 1 contains 100 parts by mass of polyol, 15 parts by mass of flame retardant 1 (melamine powder), 4.3 parts by mass of foaming agent (water), 1.1 parts by mass of foam stabilizer, and 0.18 part by mass of amine catalyst. It was obtained from a foamed polyurethane resin composition consisting of parts by mass, metal catalyst 2 (stannous octoate) 0.31 parts by mass, and an isocyanate index of 103. The foamed polyurethane layer of Comparative Example 1 has a density of 24.6 kg/m ³ , a tensile strength of 70 kPa, and an elongation of 97%.

In the laminate of Comparative Example 1, a coating layer was adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 1, and the combustion distance was 10 mm, the combustibility was judged to be "self-extinguishing", the VOC value was 446 ppm, and the FOG value was 43 ppm. , VOC, etc., and an overall evaluation of "x". Comparative Example 1 does not contain a phosphorus-containing solid flame retardant in the flame retardant and does not contain tin ricinoleate containing an active hydrogen group in the metal catalyst, so it is inferior in flame retardancy and has high VOC.

(Comparative example 2)
The foamed polyurethane layer of Comparative Example 2 contains 100 parts by mass of polyol, 20 parts by mass of flame retardant 1 (melamine powder), 4.7 parts by mass of foaming agent (water), 1.1 parts by mass of foam stabilizer, and 0.18 part by mass of amine catalyst. It was obtained from a foamed polyurethane resin composition consisting of parts by mass, metal catalyst 2 (stannous octoate) 0.31 parts by mass, and an isocyanate index of 103. The foamed polyurethane layer of Comparative Example 1 has a density of 25.5 kg/m ³ , a tensile strength of 56 kPa, and an elongation of 64%.

In the laminate of Comparative Example 2, a coating layer was adhered to one side of the foamed polyurethane layer with the hot melt adhesive 1, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 434 ppm, the FOG value was 61 ppm, The evaluation of VOC and the like is "x", and the overall evaluation is "x". In Comparative Example 2, the melamine powder content was higher than in Comparative Example 1, so the combustibility was judged to be "non-combustible." is.

(Comparative Example 3)
In the foamed polyurethane layer of Comparative Example 3, 0.31 parts by mass of metal catalyst 2 (stannous octylate) was used instead of metal catalyst 1 (tin ricinoleate containing an active hydrogen group) in Example 1, and other operations were performed. This example is the same as Example 1. The foamed polyurethane layer of Comparative Example 3 has a density of 25.6 kg/m ³ , a tensile strength of 114 kPa, and an elongation of 206%.

The laminate of Comparative Example 3 had a coating layer adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 1, and had a combustion distance of 0 mm, a combustibility judgment of "noncombustible," a VOC value of 639 ppm, an FOG value of 78 ppm, The evaluation of VOC and the like is "x", and the overall evaluation is "x". Compared with Example 1, Comparative Example 3 did not contain metal catalyst 1 (tin ricinoleate containing an active hydrogen group), so the VOC value was extremely large.

(Comparative Example 4)
In the foamed polyurethane layer of Comparative Example 4, 4 parts by mass of flame retardant 3 (phosphorus-containing liquid flame retardant) was used in place of 4 parts by mass of flame retardant 2 (phosphorus-containing solid flame retardant) in Example 2, and other 2 is the same example. The foamed polyurethane layer of Comparative Example 4 has a density of 24.8 kg/m ³ , a tensile strength of 105 kPa, and an elongation of 201%.

In the laminate of Comparative Example 4, a coating layer was adhered to one side of the polyurethane foam layer with the hot melt adhesive 1, and the combustion distance was 0 mm, the combustibility was determined to be "noncombustible," the VOC value was 219 ppm, the FOG value was 1242 ppm, The evaluation of VOC and the like is "x", and the overall evaluation is "x". Compared with Example 2, Comparative Example 4 used flame retardant 3 (phosphorus-containing liquid flame retardant) instead of flame retardant 2 (phosphorus-containing solid flame retardant), so the VOC value and FOG value were very large. rice field.

(Comparative Example 5)
The foamed polyurethane layer of Comparative Example 5 was obtained from the same foamed polyurethane resin composition as that of Example 3, and had the same physical properties as those of the foamed polyurethane layer of Example 3.

The laminate of Comparative Example 5 had a coating layer adhered to one side of the foamed polyurethane layer by flame lamination, had a combustion distance of 0 mm, and was evaluated as "noncombustible," but had a VOC value of 260. The evaluation of VOC and the like is "x", and the overall evaluation is "x". Compared to Example 3, Comparative Example 5 had a very large VOC value because adhesion was performed by frame lamination.

(Comparative Example 6)
The foamed polyurethane layer of Comparative Example 6 was obtained from the same foamed polyurethane resin composition as that of Example 3, and had the same physical properties as those of the foamed polyurethane layer of Example 3.

The laminate of Comparative Example 6 had a coating layer adhered to one side of the foamed polyurethane layer with the hot-melt adhesive 5, had a combustion distance of 0 mm, and was evaluated as "noncombustible," but had a VOC value of 128 ppm. The FOG value was 219 ppm, the TVOC value was 16 μgC/g, the VOC evaluation was “×”, and the comprehensive evaluation was “×”. Compared with Example 3, Comparative Example 6 used a hot-melt adhesive different from the polyurethane hot-melt adhesive of the present invention, so the VOC value and FOG value were significantly increased.

Thus, the laminates of Examples 1 to 6, in which the coating layer was adhered to one side of the foamed polyurethane layer of the present invention with the polyurethane hot-melt adhesive of the present invention, have low VOC and good flame retardancy. Therefore, it is suitable as a member constituting a skin material of an interior material for a vehicle.
Furthermore, since the laminates of Examples 1 to 6 have low VOC and good flame retardancy, the surface layer made of genuine leather, synthetic leather, fabric, etc. is bonded with the polyurethane hot melt adhesive of the present invention. The laminate obtained by this method also has low VOC and good flame retardancy as compared with a laminate having a surface layer adhered by a frame laminate, and is suitable as a skin material for vehicle interior materials.

REFERENCE SIGNS LIST 10, 20 Laminate 11 Polyurethane Foam Layer 13, 17 Polyurethane Hot Melt Adhesive 15 Coating Layer 19 Surface Layer

Claims (7)

A laminate obtained by laminating a covering layer on a polyurethane foam layer obtained from a polyurethane foam resin composition containing a polyol, a polyisocyanate, a foaming agent, a catalyst and a flame retardant,
The foamed polyurethane resin composition contains tin ricinoleate containing an active hydrogen group as the catalyst and a phosphorus-containing solid flame retardant as the flame retardant,
The foamed polyurethane layer and the coating layer are bonded with a polyurethane hot-melt adhesive containing a polyurethane prepolymer made from a polyol component (A) and a polyisocyanate (B),
The polyurethane prepolymer in the polyurethane hot-melt adhesive has, as the polyol component (A), a number-average molecular weight of 1000 , which is a condensation reaction of an aliphatic dicarboxylic acid having 10 to 12 carbon atoms and an aliphatic diol having 4 to 6 carbon atoms. above crystalline polyester polyol (a-1) and a polyether polyol (a-2) having a number average molecular weight of 1000 or more, and the content of the polyether polyol (a-2) in the polyol component (A) A laminate, characterized in that the amount thereof is 30 to 80 parts by mass with respect to 100 parts by mass of the polyol component (A). 2. The laminate according to claim 1, wherein the flame retardant in the foamed polyurethane resin composition includes the phosphorus-containing solid flame retardant and melamine powder having an average particle size of 0.1 to 0.5 μm. . 3. The laminate according to claim 1, wherein the phosphorus-containing solid flame retardant in the foamed polyurethane resin composition is a phosphate ester compound. The crystalline polyester polyol (a-1) of the polyurethane prepolymer in the polyurethane hot melt adhesive has a number average molecular weight of 1,000 to 5,000, and the polyether polyol (a-2) has a number average molecular weight of 1,000. 4. The laminate according to any one of claims 1 to 3, characterized in that it is ∼4000. The polyol component (A) of the polyurethane prepolymer in the polyurethane hot melt adhesive is selected from the group consisting of amorphous polyester polyols, polycarbonate polyols, and low molecular weight diols having a molecular weight of 500 or less as other polyols (a-3). 5. A laminate according to any one of claims 1 to 4, comprising one or more selected polyols. 6. The laminate according to any one of claims 1 to 5, wherein a surface layer is adhered to a surface of the foamed polyurethane layer opposite to the covering layer with the polyurethane hot-melt adhesive. 7. A skin material for vehicle interior materials, which is obtained by using the laminate according to claim 6.

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