JP2001114911A - Upholstery for automobile interior trim - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an upholstery for automobile interior trim made from a thermoplastic resin which does not emit a poisonous gas at the incineration, has an excellent recyclability and has a texture similar to that of a natural leather. SOLUTION: This material is composed of a composite resin composition comprising a polyester block copolymer resin as a main component and an acrylic type core-shell copolymer resin as a softening component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a halogen-free resin material for automobile interiors, which has surface abrasion and chemical resistance.
The present invention relates to a polyester synthetic leather excellent in flexibility and a skin material for an automobile interior.

[0002]

2. Description of the Related Art Conventionally, soft polyvinyl chloride resins have been mainly used as synthetic leathers and seat materials used for interiors of automobiles and the like, and have been used for a long time because of their excellent workability, paintability and various physical properties. Has been used.

However, in recent years, the treatment of halogen-containing organic compounds and hydrogen halide compounds generated during the incineration and disposal of plastics has become a problem from the viewpoint of environmental protection, and halogen-free products that replace polyvinyl chloride resin that requires specific incineration equipment have become a problem. There has been a demand for a resin-made sheet or synthetic leather.

Synthetic leather for upholstery of automobiles has an uneven pattern (referred to as a grain pattern) imitating the appearance of natural leather, is required to have flexibility and strength similar to that of natural leather, and is sewn by sewing. Needs sewing workability and sewing strength because it is shaped according to the chair shape, is reinforced by lining a rayon fiber or polyester fiber woven or non-woven fabric, and has at least a two-layer structure of a resin sheet skin and a base cloth This is usually the case.

[0005] Conventional synthetic leather mainly uses a vinyl chloride resin as a skin material, and is a laminate with a different kind of resin material such as polyester fiber cotton. Re-melting and recycling the laminate as it is is the melting temperature of the two materials,
It is practically difficult due to the different decomposition temperature and affinity, and requires separation processing. However, it is difficult to completely separate the fiber fuzz and the like, resulting in a remarkable reduction in the physical properties and appearance of the recycled product and an obstacle in terms of cost.

[0006] Therefore, it is desired to produce a recyclable laminated structure by integrating the sheet material resin with a polyester resin which is a raw material of a fiber cotton used as a base cloth. However, polyethylene terephthalate resin of polyester for fibers is rigid when formed into a film, has no flexibility, and is unsuitable as a synthetic leather skin resin.

When a polyester block copolymer is considered as a substitute for a soft vinyl chloride resin from the viewpoint of a flexible polyester, that is, a polyester elastomer, the polyester block copolymer is excellent in mechanical strength and impact resistance, but has a high mechanical strength and impact resistance. Compared with thermoplastic elastomers, they still have a high elastic modulus and are relatively hard, so that it is difficult to substitute soft polyvinyl chloride resin for synthetic leather.

[0008] The soft polyvinyl chloride resin has a glass transition temperature near room temperature, a large loss coefficient near room temperature, and a small rubber-like rebound resilience, and thus has the characteristic of being similar to leather in flexibility. In contrast, Japanese Patent Laid-Open No.
38546 and JP-A-2-43251 disclose methods of blending a plasticizer for softening the polyester block copolymer, or blending a natural or synthetic rubber. Since the softened resin composition has a glass transition temperature sufficiently lower than room temperature and a small loss coefficient near room temperature, it generates rubber-like resilience and lacks flexibility similar to leather.

[0009]

SUMMARY OF THE INVENTION The present invention provides a flexible, comfortable seat, heat resistance, light resistance, abrasion resistance, oil resistance,
An object of the present invention is to provide an upholstery material having excellent mechanical properties and good recyclability.

[0010]

Means for Solving the Problems The inventors of the present invention have made intensive studies to give a texture and flexibility similar to soft polyvinyl chloride to a polyester block copolymer, and as a result, a specific core / shell copolymer has been blended. The present invention has found that the obtained polyester block copolymer is soft and has a low elastic modulus, has a glass transition temperature near room temperature, has a large loss coefficient near room temperature, and obtains a supple texture like a soft polyvinyl chloride resin. Reached.

That is, the gist of the present invention is that 90 to 20 parts by weight of the component (A) polyester block copolymer is added to the component (B).
A colorant in a polyester block copolymer composition containing 10 to 80 parts by weight of an acrylic core / shell copolymer,
Synthetic leather obtained by molding and processing a polyester resin composition mixed with an inorganic filler, a lubricant, and a light-heat stabilizer by a conventional method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The synthetic leather made of the polyester elastomer according to the present invention does not necessarily require a fibrous base fabric depending on the application, and may be used alone. However, in many cases, (a) the fibrous base fabric and (b) the saturated fabric are used. An adhesive layer of a reactive paint containing a polyester resin or isocyanate and (c) a specific polyester block copolymer composition as a skin layer; (c) a saturated polyester resin, an acrylate resin on the surface of the polyester elastomer layer; And a paint layer such as a polyurethane resin.

(A) Fibrous base fabric The fibrous base fabric is made of natural fibers such as cotton and hemp, regenerated fibers such as viscose rayon, polyamide fibers, acrylic fibers,
Synthetic fibers such as polyester fibers are exemplified. The fiber may have any shape such as a spun short fiber yarn or a long fiber yarn. The base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. Of these, polyester fiber cloth is most preferred. (B) Adhesive layer The adhesive layer is used when the base fabric and the skin layer are firmly integrated. A small amount of a paint containing a saturated polyester resin and a polyurethane resin is applied to a base fabric or a skin sheet with a roll coater or the like, and then processed by heating and drying, or hot melt coated. (C) Polyester Elastomer Surface Layer The polyester elastomer surface layer is composed of a polyester block copolymer composition, and the polyester block copolymer composition is composed of a high melting crystalline polymer segment (a1) mainly composed of crystalline aromatic polyester units. )
And a polyester block copolymer (A) having a low melting point polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit as a main component, butyl acrylate alone or butyl acrylate -Ethylhexyl acrylate mixture (b1), at least one compound selected from alkyl acrylates and alkyl methacrylates having an alkyl group having 1 to 4 carbon atoms (b
2), a vinylcyan compound (b3), the following structural formula (I)
A monoalkyl maleate compound represented by the formula (b)
4) and a polymer obtained by emulsion polymerization of the crosslinking agent (b5) as a core, and a polymer obtained by polymerizing an aromatic vinyl compound (b6), a vinylcyan compound (b3), and a crosslinking agent (b5) as a shell. Core-shell copolymer (B)
One or two or more kinds of the polyester block copolymer (A) and the core-shell copolymer (B) in a weight ratio of (A) :( B) = 90: 10
~ 20: 80,

[0015]

Embedded image (Wherein, the substituent R represents a saturated aliphatic hydrocarbon group having 10 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.) Further, the polyester block copolymer (A) One or more compounds (C) and / or silicon compounds (D) selected from calcium carbonate, silica, fluororesin, talc, and mica are added in an amount of 0.01 to 100 parts by weight of the composition.
20 parts by weight of red phosphorus and ammonium polyphosphate compound microencapsulated by coating the surface with a resin as a flame retardant (E) in 100 parts by weight of the polyester block copolymer composition (A) And 0.01 to 50 parts by weight of one or more compounds selected from organic phosphoric acid compounds and organic phosphorous acid compounds, and (b) in the core-shell copolymer (B).
The copolymerization amount of 1) is 40 to 80% by weight, the copolymerization amount of (b2) is 3 to 35% by weight, the copolymerization amount of (b3) is 4 to 30% by weight, and the copolymerization amount of (b4) is 0. 0.5 to 8% by weight, the copolymerization amount of the crosslinking agent (b5) is 0.25 to 8% by weight, and the copolymerization amount of the aromatic vinyl compound (b6) is 3 to 20% by weight. 6 to 20 parts by weight of an aromatic vinyl compound (b6), 3 to 12 parts by weight of a vinyl cyanide compound (b3), and 0.05 to 1 part by weight of a crosslinking agent (b5) are polymerized with 100 parts by weight of the compound. A core-shell copolymer having the polymer obtained as a shell, the amount of 2-ethylhexyl acrylate in the mixture (b1) being 40% by weight or less, and the structural formula (I) The substituent R is a saturated aliphatic hydrocarbon group having 10 to 24 carbon atoms, Wherein the crosslinking agent (b5) is a dihydric or triacrylate of a polyhydric alcohol, a dimethacrylate or trimethacrylate of a polyhydric alcohol, or an aromatic group. At least one compound selected from divinyl compounds, the high-melting crystalline polymer segment (a1) is mainly composed of polybutylene terephthalate units, and the low-melting polymer segment ( a2) is composed of a poly (tetramethylene oxide) glycol unit;
It is a preferable condition that the copolymerization amount of the low melting point polymer segment (a2) in the polyester block copolymer (A) is 40 to 90% by weight. You can expect to get excellent effects.

The high-melting crystalline polymer segment (a) of the polyester block copolymer (A) used in the present invention.
1) is a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol, preferably terephthalic acid and / or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol. In addition, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sulfo A dicarboxylic acid component such as isophthalic acid or an ester-forming derivative thereof;
00 or less diols, for example, aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol;
Alicyclic diols such as cyclohexane dimethanol and tricyclodecane dimethylol, xylylene glycol,
Bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4-
(2-hydroxyethoxy) phenyl] sulfone, 1,
1-bis [4- (2-hydroxyethoxy) phenyl]
Polyesters derived from aromatic diols such as cyclohexane, 4,4'-dihydroxy-p-terphenyl and 4,4'-dihydroxy-p-quarterphenyl, or two or more of these dicarboxylic acid components and diol components Co-polyesters used in combination may be used. Further, a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component,
It is also possible to copolymerize in the range of mol% or less.

The low-melting polymer segment (a2) of the polyester block copolymer (A) used in the present invention comprises:
An aliphatic polyether and / or an aliphatic polyester. Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). Examples include an ethylene oxide addition polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Examples of the aliphatic polyester include poly (ε-caprolactam), polyenantholactone, polycaprolactam, polybutylene adipate, and polyethylene adipate. From the elastic properties of the polyester block copolymer obtained from these aliphatic polyethers and / or aliphatic polyesters, poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, poly (ε-caprolactam) ), Polybutylene adipate, polyethylene adipate and the like are preferable, and among these, poly (tetramethylene oxide) glycol is particularly preferable. Further, the number average molecular weight of these low melting point polymer segments is preferably about 300 to 6000 in a copolymerized state.

The low melting point polymer segment (a) in the polyester block copolymer (A) used in the present invention
The copolymerization amount of 2) is preferably 40 to 90% by weight, more preferably 50 to 85% by weight.

The polyester block copolymer (A) used in the present invention can be produced by a known method.
For example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low-molecular-weight glycol, and a low-melting polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the obtained reaction product. Alternatively, a dicarboxylic acid, an excess amount of glycol and a low melting polymer segment component are subjected to an esterification reaction in the presence of a catalyst, and the resulting reaction product is polycondensed. A method in which a high-melting-point crystalline segment is prepared in advance, and a low-melting-point segment component is added to the segment to make it random by transesterification, and a method in which the high-melting-point crystalline segment and the low-melting-point polymer segment are connected with a chain linking agent. . Further, when poly (ε-caprolactam) is used for the low-melting-point polymer segment, any method may be employed, such as adding ε-caprolactam monomer to the high-melting-point crystalline segment.

The core-shell copolymer (B) used in the present invention comprises butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b)
1) at least one compound (b2) selected from alkyl acrylates and alkyl methacrylates having an alkyl group having 1 to 4 carbon atoms, a vinyl cyanide compound (b3), represented by the following structural formula (I) A polymer obtained by emulsion polymerization of a maleic acid monoalkyl ester compound (b4) and a crosslinking agent (b5) is used as a core, and an aromatic vinyl compound (b6), a vinylcyan compound (b3), and a crosslinking agent (b5) are further added. It is a core-shell copolymer in which the polymer obtained by polymerization is a shell.
1 to 4 carbon atoms constituting the core of the shell copolymer (B)
Examples of the acrylate and methacrylate (b2) having an alkyl group of (b2) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Ethyl acrylate, methyl methacrylate, and ethyl methacrylate can be preferably used.

[0021]

Embedded image (Wherein, the substituent R is a saturated aliphatic hydrocarbon group having 10 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group)

As the vinyl cyan compound (b3) constituting the core-shell copolymer (B) used in the present invention, acrylonitrile, methacrylonitrile and the like can be used.

The monoalkyl maleate compound (b4) constituting the core-shell copolymer (B) used in the present invention is represented by the above structural formula (I), and the saturated aliphatic hydrocarbon group is Lauryl, undecanyl, myristyl, palmityl, heptadecanyl, stearyl, arachidyl, behenyl and the like. As unsaturated aliphatic hydrocarbon groups, palmitoleyl group, heptadecenyl group, oleyl group, eicosenyl group,
An enolesyl group, a linole group, a linolenic group and the like can be mentioned. Examples of the aromatic hydrocarbon group include a phenylpropane group, a phenylsulfone group, a xylyl group, and a naphthyl group. Further, examples of the alkali metal include sodium and potassium.

The crosslinking agent (b5) constituting the core-shell copolymer (B) used in the present invention includes ethylene glycol, diethylene glycol, triethylene glycol, 2,3 propanediol, 1,4-butanediol, Examples thereof include diacrylates and / or triacrylates of polyhydric alcohols such as glycerin, and aromatic divinyl compounds such as dimethacrylate and / or trimethacrylate of similar polyhydric alcohols, divinylbenzene, and divinyltoluene.

The aromatic vinyl compound (b6) constituting the core-shell copolymer (B) used in the present invention includes styrene, α-methylstyrene, o-methylstyrene, m-methoxystyrene, N, N -Dimethyl-p-aminostyrene, divinylbenzene and the like.

The amount of butyl acrylate alone or the mixture of butyl acrylate and 2-ethylhexyl acrylate (b1) constituting the core-shell copolymer (B) used in the present invention is determined by the amount of the core-shell copolymer (B). )
Butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1), preferably 40 to 80% by weight per 100% by weight
If the copolymerization amount is less than 40% by weight, the flexibility of the core-shell copolymer (B) is insufficient, and the flexibility of the polyester block copolymer composition as the object of the present invention cannot be sufficiently achieved. When the copolymerization amount of butyl acrylate alone or a mixture of 2-ethylhexyl acrylate (b1) exceeds 80% by weight, the core-shell copolymer (B)
, The polyester block copolymer composition of the present invention has tackiness, and a texture similar to the intended soft polyvinyl chloride resin cannot be achieved.

The amount of 2-ethylhexyl acrylate in the butyl acrylate alone or the mixture of butyl acrylate and 2-ethylhexyl acrylate (b1) constituting the core-shell copolymer (B) used in the present invention is 40% by weight or less. Preferably, there is. When the amount of 2-ethylhexyl acrylate exceeds 40% by weight, the tackiness of the core-shell copolymer (B) becomes remarkable, so that the polyester block copolymer composition of the present invention has tackiness, A feeling similar to soft polyvinyl chloride resin cannot be achieved.

The shell constituting the core-shell copolymer (B) used in the present invention comprises 6 to 20 parts by weight of an aromatic vinyl compound (b6) and 100 parts by weight of a vinyl cyanide compound based on 100 parts by weight of the core polymer. It is preferable that 3 to 12 parts by weight of b3) and 0.05 to 1 part by weight of the crosslinking agent (b5) are polymerized. When the amount of the aromatic vinyl compound (b6) or vinyl cyan compound (b3) constituting the shell polymer is small, the dispersion of the core / shell copolymer (B) in the polyester block copolymer (A) is poor, The strength of the polyester block copolymer composition comprising them is significantly reduced. Also, when the amount of the aromatic vinyl compound (b6) or vinyl cyanide compound (b3) constituting the shell polymer is large, the flexibility of the core-shell copolymer (B) is insufficient, which is an object of the present invention. Softening of the polyester block copolymer composition cannot be sufficiently achieved.

The amount of the core / shell copolymer (B) to be blended with the polyester block copolymer (A) of the present invention is (A) :( B) = 90: 10 to 2 in weight ratio.
0:80 is preferable. If the amount of the core-shell copolymer (B) is less than this range, the polyester block copolymer composition, which is the object of the present invention, cannot be sufficiently softened. Further, when the blending amount of the core-shell copolymer (B) is larger than this range, the strength of the polyester block copolymer composition is undesirably reduced.

The one or more compounds (C) and / or silicone compounds (D) selected from calcium carbonate, silica, fluororesin and mica used in the present invention are composed of a polyester block copolymer (A) and a core / shell compound. When the blending amount of the copolymer (B) is (A) :( B) =
90:10 to 20:80, preferably 100 to 100 parts by weight of the polyester block copolymer composition.
0 parts by weight, more preferably 0.05 to 15 parts by weight, is blended. By blending these, the smoothness of the polyester block copolymer composition of the present invention, which is similar to the soft polyvinyl chloride resin and has no stickiness, is further emphasized. Known materials can be used for at least one compound (C) and / or silicone compound (D) selected from calcium carbonate, silica, fluororesin, and mica. As the silicone compound, silicone oil, gum-like silicone resin, silicone resin and the like can be used.

Since the polyester block copolymer composition of the present invention is intended to replace a soft polyvinyl chloride resin having excellent flame retardancy, a flame retardant may be blended in applications requiring flame retardancy. It is necessary to impart flammability, while the polyester block copolymer composition of the present invention is characterized by being a resin containing no halogen atom,
The flame retardant (E) is not a flame retardant by the conventional combination use of an organic halogen compound and antimony trioxide, but a red phosphorus, an ammonium polyphosphate compound, a trimethyl phosphate, a trimethyl phosphate, a microencapsulated by covering the surface with a resin. One or more compounds selected from organic phosphoric acid compounds such as phenyl phosphate and organic phosphorous compounds such as trimethyl phosphite and triphenyl phosphite are preferred. In these flame retardants (E), the blending amounts of the polyester block copolymer (A) and the core-shell copolymer (B) are (A) :( B) = 90: 10 to 20:80 in weight ratio. 100 parts by weight of the polyester block copolymer composition, preferably 0.01 to 50 parts by weight, more preferably 0.05 to
-30 parts by weight are blended.

The method for producing the polyester block copolymer composition of the present invention is not particularly limited. For example, the polyester block copolymer (A), the core-shell copolymer (B), and At least one compound selected from calcium carbonate, silica, fluorine resin, talc and mica (C), silicon compound (D) and red phosphorus and ammonium polyphosphate microencapsulated by covering the surface with a resin A method in which a raw material in which other additives including one or more flame retardants (E) selected from a compound, an organic phosphoric acid compound, and an organic phosphorous acid compound are blended together is supplied to a screw-type extrusion and melt-kneaded; And the polyester block copolymer (A) is supplied to the screw type extruder and melted, and the core / shell copolymer (B) and The core-shell copolymer (B) is supplied to a screw-type extruder and melted, and the polyester block copolymer (A) and other additives are further supplied from another supply port. A method of supplying and kneading may be used. Further, all or a part of the additives other than the polyester block copolymer (A) and the core / shell copolymer (B) may be preliminarily added to the polyester block copolymer (A) or the core / shell copolymer (B). And melt-mixing them in a screw type extruder.

The polyester block copolymer composition of the present invention may contain a known antioxidant such as a hindered phenol, phosphite, thioether or aromatic amine as long as the object of the present invention is not impaired. , Benzophenone-based, benzotriazole-based, hindered amine-based light stabilizers, pigments, dyes and the like can be arbitrarily contained.

Such a mixed resin composition is melt-molded. For example, the mixed resin composition is introduced into an extruder, etc., heated and melted and extruded into a sheet shape by a T-die to obtain a fiber cloth or a plastic base. Press-pressing in a pressurized state with the material, a so-called melt extrusion method, or melt-kneading the mixed resin composition between two heated metal rolls, passing through a heating calender, forming a sheet to a predetermined thickness, The sheet is formed by a so-called calender method or the like, but other known molding methods (including plastic molding) can also be adopted and are not particularly limited.

The surface of the molded skin material of the present invention can be subjected to resin processing according to the purpose. With such resin processing,
It imparts scratch resistance or a leather-like surface touch, and preferably uses a urethane resin.

The resin processing can be performed by a known method such as a gravure coater or a knife coater. The thickness of the resin layer in the resin processing is preferably 3 to 40.
μm, more preferably in the range of 5 to 20 μm.

As a method for imparting a leather-like pattern to the surface of the polyester-based natural leather-like sheet of the present invention, for example, the leather pattern is simultaneously pressed and pressed between a molten sheet of the mixed resin composition and a substrate. It can be applied by using an embossing roll or a female pattern paper having the resin composition, or after the mixed resin composition is formed into a sheet, while the sheet is ripened, by using the embossing roll or the release paper. In any case, a pattern can be imparted by employing these known methods.

Further, the mixed resin composition of the present invention may contain other resins, coloring agents, flame retardants, anti-sonoic agents, moisture absorbing and releasing agents, extenders and ultraviolet absorbers within a range not to impair the effects of the present invention. May be mixed.

[0039]

EXAMPLES The effects of the present invention will be described below with reference to examples. The percentages and parts in the examples are all based on weight unless otherwise specified.

The details of the physical property evaluation methods shown in the examples are as follows. (1) Hardness: based on JIS K-6301 (A standard). As a test piece for hardness measurement, the pellets obtained in the step 1 (manufacture of a thermoplastic elastomer) were compression-molded to a thickness of 2 mm, and three of them were stacked. (2) Sheet flexibility: viscoelasticity measuring device (DVE Rheospectoller DVE-V4 manufactured by Rheology)
(Type) The elastic modulus and the loss rate when heated at a heating rate of 3 ° C./min were measured. (3) Mechanical properties test Tensile strength, elongation, tear strength, and peel strength conform to JIS K6772 vinyl leather cloth test method. Tensile speed 2 under conditions of 20 ° C and 65% RH
A tensile test was performed at 00 mm / min. (4) Thermal stability test After the sheet was stored in a gear oven (manufactured by Toyo Seiki) heated to 100 ° C. for 600 hours, a dumbbell piece was cut out, and the thermal stability was evaluated from tensile strength and tensile elongation at break. (5) Light Resistance Test After irradiating the sheet with light up to 200 MJ in a xenon arc lamp weather meter (Ci65 manufactured by Atlas), a dumbbell piece was cut out, and light resistance was evaluated based on tensile strength and elongation at break. (6) After storing the wet heat aging test sheet in a low temperature and constant temperature and humidity machine (manufactured by Tabai Seisakusho) set at 70 ° C. and 95% RH for 600 hours, a dumbbell piece is cut out, and moisture and heat resistance is determined from tensile strength and elongation at break. Was evaluated. (7) In the abrasion resistance test, No. 6 cotton canvas was repeatedly subjected to plane friction under a load of 1 kg, and slid 10,000 times. (8) Cold resistance test conforms to JIS K6772. At −35 ° C., no crack was evaluated as ○, and existence was evaluated as x. (9) Kneading test Based on JIS K6772, when there was no abnormality at 1,000 times with a load of 1 kgf 1,000 times, it was evaluated as ○.

Raw Materials for Sheet-shaped Molded Product (A) Component 234 parts of terephthalic acid, 1,4-butanediol 215
Polyester block copolymer (A-1) synthesized by adding 2 parts of titanium tetrabutoxide to 723 parts of poly (tetramethylene oxide) glycol having about 2000 parts by weight and a number average molecular weight of about 2,000. 0.46 kg of decyl monoester, 0.16 k of 50% aqueous solution of potassium hydroxide
g, sodium dodecylbenzenesulfonate 0.031
kg, butyl acrylate 9 kg, methyl acrylate 2.6 kg, acrylonitrile 1.3 kg, 1,4-butanediol dimethacrylate 0.19 kg, t-dodecylmercaptan 0.039 kg, potassium persulfate 0.1 kg.
After charging 029 kg into a reaction vessel and reacting at 60 ° C. for 2 hours and 30 minutes, 2.7 kg of styrene, 0.74 kg of acrylonitrile, 0.025 kg of divinylbenzene, and 0.005 kg of t-dodecyl mercaptan were added to the latex of the core polymer obtained. Core-shell copolymer (B-1) obtained by adding to a reaction vessel and performing a reaction Other optional components Calcium carbonate (C) and silicone resin (D), weather stabilizer, antioxidant, Various additives such as pigments.

Production of Sheet-like Molded Article (1) Molding The above-mentioned thermoplastic elastomer is molded into a sheet after blending the above-mentioned components (A) to (D) if desired.
Generally, it is formed into a sheet by an ordinary method using an extruder or a press forming machine equipped with a calender roll, a T die or an annular die. For embossing (embossing), a sheet formed from an extruder equipped with a calender roll or T die is melted or semi-molten as it is between the crimping roll (embossing) and a pressure roll such as a rubber roll. A method in which a pre-wound sheet is reheated by a heating drum and an infrared heater, and is similarly passed between a crimping roll (embossing pattern) processing roll and a pressure roll such as a rubber roll, intermittently (embossing) embossing. A method of pressing a sheet using a mold with a pattern is employed. Also, a method of embossing (embossing) the sheet at the same time as shaping the sheet by vacuum forming using a female mold having (embossed) embossed pattern is included. Further, the present invention also includes a sheet obtained by laminating a foam or the like on the embossed (embossed) sheet and forming the sheet by vacuum forming or the like of a female draw. In addition, the embossed pattern (embossed pattern) is a state in which the surface of the sheet is embossed into an embossed pattern such as leather or geometric shape. (2) Sheet-shaped molded article The sheet is usually about 0.05 to 10 mm in thickness. A foam, woven fabric, nonwoven fabric, cotton fabric, paper, or the like can be laminated on the sheet, and a coat layer can be applied to at least one surface of the sheet. Further, those obtained by shaping these sheets and their laminates by vacuum forming, pressure forming, etc. are also included in the present invention. (3) Use The skin material for an automobile interior of the present invention is a sheet-like molded body with a textured (embossed pattern) having an embossed pattern such as a leather or a geometric shape. Seat material used for interior parts in automotive parts, in particular, automotive parts, specifically, skin materials such as instrument panels, door trims, console boxes, ceiling seats, handle pads, seat seats, etc. Can be used.

Example 1 A core-shell copolymer (B-1), calcium carbonate (C component: Super S manufactured by Maruo Calcium Co., Ltd.), and a silicone resin (D component: Toray Dow Corning's BY270106), a pigment, and stabilizers were mixed at a mixing ratio shown in Table 1 using a V-blender, and heated at 210 ° C. using a twin-screw extruder having a 45 mm diameter, three-threaded screw. Melt kneading,
Pelletized (Step 1: production of polyester elastomer). This polyester elastomer pellet is
Using a mmφT die extruder (L / D28 single screw extruder manufactured by Thermoplastics Industries), 2
A sheet having a thickness of 1.0 mm was prepared at a temperature of 00 ° C. (Step 2-1: Production of a sheet-like molded product). The sheet was cut out into a 5 mm wide × 30 mm long tank shape to obtain a test piece. Table 1 shows the physical properties measured using this test piece.

Example 2 As shown in Table 1, the same experiment as in Example 1 was conducted except that the mixing ratio of the component (A-1) and the component (B-1) was different. Table 1 shows the obtained physical properties.

Comparative Example 1 As shown in Table 1, component (A-1), component (B-1),
The same experiment as in Example 1 was conducted, except that only the component (A-1) was used among the four components C and D.
Table 1 shows the obtained physical properties.

Comparative Example 2 A soft vinyl chloride resin sheet compounded by Kyowa Leather Co., Ltd. (a vinyl compound compounded by Kyowa Leather Co., Ltd.), which is practically used as a synthetic leather for pasting a chair,
After kneading at a surface temperature of 170 ° C with an inch diameter mill roll,
A sheet was formed to a thickness of 1.0 mm by a hot press at 170 ° C. to obtain a sample. Table 1 shows the physical properties obtained by preparing the same test pieces as in Example 1.

[0047]

[Table 1]

The polyester block copolymer composition of the present invention shown in the examples has a lower elastic modulus near room temperature than the base polyester block copolymer, indicating that it is soft. . It is also clear that the loss rate near room temperature is large and the rebound resilience is low.

The commercial polyester elastomers shown in Comparative Examples have a high elastic modulus near room temperature and a low loss rate.
It is evident that the level is insufficient as a resin for the material for pasting chairs for automobile interiors.

Therefore, the polyester block copolymer composition of the present invention is not only flexible and has a low elastic modulus, but also has a smooth and supple texture like a soft polyvinyl chloride resin.

Example 3 A polyester elastomer was produced in exactly the same manner as in Step 1 of Example 1 and then heated to 200 ° C. using a 90 mm φT die extruder in the same manner as in Step 2-1 of Example 1 above.
At a temperature of 0.7 mm. The sheet was coated with a urethane-based top coat (Rack Skin U803, manufactured by Seiko Chemical Co., Ltd.) using a wet coat of 40 g / m ² roll coater, dried and gloss-adjusted, and then subjected to a laminating press with an infrared heater. 1.4m
An m-thick embossed sheet was manufactured (Step 2-2: Manufacture of embossed sheet). Dumbbell 1 with this textured sheet
A stamping aging test was performed on the No. 2 shape. Table 2 shows the results.

Comparative Example 3 The same aging test as in Example 3 was performed using a soft PVC sheet for a molded chair (a thermoforming sheet with a 1.8 mm-thick grain, manufactured by Kyowa Leather Co., Ltd.). Table 2 shows the results.

[0053]

[Table 2]

From Example 3 and Comparative Example 3, it was confirmed that there was no problem in long-term use.

Example 4 After a polyester elastomer was produced in exactly the same manner as in Step 1 of Example 1, the polyester elastomer was prepared at 200 ° C. using a 90 mmφT die extruder in the same manner as in Step 2-1 of Example 1 above.
At a temperature of 0.3 mm. A urethane-based top coat (Rack Skin U551M, manufactured by Seiko Kasei Co., Ltd.) was applied to this sheet with a wet coat weight of 40 g / m ^{2 using a} roll coater and dried, and then a urethane-based adhesive was applied to the back of the sheet using a hot drum laminator with a roll coater. An agent (Seika Bond HW311 manufactured by Dainichi Seika Co., Ltd.) was applied at a wet weight of 40 gr / m ² , laminated with a double-sided knitted fabric of 30th polyester fiber yarn, and further, a urethane top coat 4 and an infrared heater were added to the sheet. Manufactured using a leather press (Step 2-
3: Production of a sheet with a leather-like base cloth). The obtained leather with a base cloth was tested according to the JIS vinyl leather test method. Table 3 shows the results.

Comparative Example 4 Soft PVC leather (rayon yarn 3 for automobile main sheet)
The same test as in Example 4 was conducted using a zero-th surface double-sided knitted leather (manufactured by Kyowa Leather Co., Ltd.). Table 3 shows the results.

[0057]

[Table 3]

From Example 4 and Comparative Example 4, the product of the present invention was equivalent to the performance of general-purpose leather, and a sufficiently satisfactory result was obtained as a material for attaching a chair to a car interior.

[0059]

The polyester sheet of the present invention is
No harmful gas is generated even when incinerated, it has excellent recyclability, has a texture similar to natural leather, and has high heat resistance, light resistance, and abrasion resistance, and interior materials, especially automotive interior members, such as instrument panels, It can be used advantageously for door trims, console boxes, leather seats for seats and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 55/02 C08L 55/02 67/02 67/02 // B60R 13/02 B60R 13/02 B (72 Inventor Yukio Ishihara 25, Kamitoike, Yoshiwara-cho, Toyota-shi, Aichi Prefecture Araco Co., Ltd. (72) Inventor Haruo Esaka 25-00 Kamifujiike, Yoshiwara-cho, Toyota-shi, Aichi Prefecture Araco Co., Ltd. Nagoya Office, Toray Dupont Co., Ltd. Nagoya Office (72) Inventor Teruo Maeyama 3804, Honoshizaki-cho, Minato-ku, Nagoya City, Aichi Prefecture (72) Inventor Tateo Yamamoto 1876 Higashi-cho, Hamamatsu-shi, Shizuoka Prefecture Inside Kyowa Leather Co., Ltd. (72) Takato Nakamura 1876 Higashi-cho, Hamamatsu-shi, Shizuoka Kyowa F-term within the stock company (reference) DA057 DE236 DH057 DJ016 DJ046 DJ056 EW047 EW067 FB287 FD016 FD030 FD090 FD137 FD140 GN00

Claims (4)

[Claims] 1. The mixing ratio of the polyester block copolymer (A) and the acrylic core / shell copolymer (B) is (A) :( B) = 90: 10 to 20:80 in weight ratio.
A skin material for automobile interiors, comprising a polyester block copolymer composition as a main component. 2. The compounding amount of the polyester block copolymer (A) and the acrylic core / shell copolymer (B) is (A) :( B) = 90: 10 to 20:80 in weight ratio.
A skin material for automobile interiors, comprising a mixed resin composition obtained by adding a colorant, a stabilizer, and a filler to the polyester block copolymer composition. 3. The polyester block copolymer,
The skin material for an automobile interior according to claim 1 or 2, further comprising a regenerated sheet of the resin composition. 4. A laminated body for an automobile interior, wherein a fiber cloth or a plastic foam is laminated on the surface material for the interior of the automobile.