CN1792651A - Inner decoration material for vehicle - Google Patents

Abstract

Provided is an automotive interior material capable of reducing emissions of toluene and formaldehyde. A pillar decorative material (10) as an automotive interior material is formed by sticking a flexible skin material (3) on a base material (5) made of synthetic resin through an adhesive layer (4). The skin material ( 3 ) is obtained, for example, by joining a cushioning sheet ( 2 ) made of foamed synthetic resin forming an inner layer to the back surface of a fabric forming a skin layer. The adhesive layer (4) is composed of a solvent containing esters (ethyl acetate, etc.) or ketones substantially free of toluene, a main agent containing an acrylic polymer soluble in the solvent, a crosslinking agent, and acetyl Acetone-based acrylic solvent-based adhesive formation. 0.01-2 parts by weight of acetylacetone is contained with respect to 100 parts by weight of solid content of the main ingredient.

Description

Automotive interior materials

technical field

The present invention relates to an interior decoration material such as a pillar decoration material, a door decoration material, an instrument panel, an instrument cover, a console, a roof material, etc. of an automobile. An automotive interior material formed by pasting a permanent skin material on a base material made of synthetic resin.

Background technique

In Patent Document 1, an interior material for automobiles is described, which uses an adhesive mainly composed of acrylic resin and has a viscosity of 5,000 to 20,000 mPa·s at about 20° C., and uses a fabric with an elongation of 35 to 100% as The skin material is pasted on the core material (substrate) made of synthetic resin. The material and viscosity of the adhesive are selected in consideration of adhesion strength and avoiding seepage to the surface of the fabric, without special consideration of the impact on the environment. Therefore, the components of the adhesive used in the examples are a solvent composed of toluene and ethyl acetate, a main agent composed of an acrylate polymer soluble in the solvent, and a crosslinking agent composed of an isocyanate compound.

When the adhesive is applied to the surface material and dried to form an adhesive layer, most of the toluene contained in the adhesive volatilizes. However, after the skin material is attached to the base material through the formed adhesive layer, even after it is mounted on a car, a very small amount of toluene remains in the adhesive layer, and the remaining toluene may be released into the car. In addition, the composition of the adhesive contains substances that generate formaldehyde. Even if such substances are not contained, formaldehyde contained in the air may enter the adhesive layer, or formaldehyde may be generated by heating, so formaldehyde may be released into the adhesive layer. Distributed in the car. These toluene and formaldehyde are substances that cause symptoms in so-called sick rooms, and especially in summer, the emission of these substances increases when the temperature rises, causing problems in the car.

Therefore, the inventors of the present invention have conducted research on whether it is possible to use an accelerator selected from the group consisting of urea and acetylacetone, and glyoxal and acetylacetone in the known formaldehyde reduction method. The formaldehyde scavenger selected from the group consisting of a combination with urea (Patent Document 2) uses an aldehyde adsorbent composed of an active energy ray-curable resin containing an acetylacetonate group, or uses urea, thiourea, ethylene urea, bis Scavengers composed of cyanamide, glyoxal monourethane, amines, and amides are used in adhesives for automotive interior materials.

However, urea lacks solubility in solvent-based adhesives. On the one hand, dicyandiamide and amines tend to react with so-called main ingredients in solvent-based adhesives. When dicyandiamide and amines are used, there is a problem that the adhesive lacks stability over time.

Patent Document 1: Japanese Unexamined Patent Publication No. 7-108881

Patent Document 2: Japanese Unexamined Patent Publication No. 2-232279

Patent Document 3: Japanese Unexamined Patent Publication No. H11-197501

Contents of the invention

An object of the present invention is to provide an automotive interior material capable of reducing emissions of toluene and formaldehyde.

The present invention relates to an automotive interior material formed by pasting a flexible skin material on a base material made of synthetic resin through an adhesive layer, wherein the adhesive layer contains substantially no A solvent of toluene, a main ingredient containing an acrylic polymer soluble in the solvent, a crosslinking agent, and an acrylic solvent-based adhesive formed of acetylacetone.

1. Product parts of automotive interior materials

The product part of the automotive interior material of the present invention is not particularly limited, and includes, for example, a pillar trim material, a door trim material, an instrument panel, an instrument cover, a console, a ceiling material, and the like. In addition, as will be described later, by using a cushioning material for the base material or the skin material, the automotive interior material also functions as an automotive cushioning material.

2. Substrate

The base material of interior materials for automobiles is made of synthetic resin in a shape corresponding to the part of the product mentioned above. The type of synthetic resin is not particularly limited, and examples thereof include polyethylene, polypropylene, polyester, polystyrene, polyethylene terephthalate (PET), polyvinyl chloride, nylon, polyurethane, and the like. Synthetic resins can be nearly rigid or cushioning. The synthetic resin having cushioning properties may be, for example, foamed synthetic resin or solid rubber-like elastic synthetic resin. In addition, the substrate may have a single-layer structure or a multi-layer (layered) structure (preferably 2 to 4 layers). The method of forming the substrate is not particularly limited, and examples thereof include injection molding, injection extrusion molding, RIM molding, blow molding, press molding, hollow molding, and vacuum molding.

3. Surface material

The material used for the flexible skin material of the automotive interior material is not particularly limited, for example, woven fabric, non-woven fabric, raised cloth, flocked cloth, synthetic resin sheet, rubber sheet, leather, paper, etc. can be used. In addition, the skin material may have a single-layer structure or a multi-layer (lamination) structure (preferably 2 to 4 layers). In the latter case, the same material or different types of materials may be laminated. In addition, if it is a single layer, a cushioning material or a sound-insulating material can be used in this layer, and if it is multi-layered, a cushioning material or a sound-insulating material can be used in any layer. The cushioning material is not particularly limited, and may be, for example, a foamed resin, a sheet made of elastomer or rubber, or a solid rubber-like elastic resin, a sheet made of elastomer or rubber. The sound insulating material is not particularly limited, and the sheets mentioned as the aforementioned cushioning material may also be used as the sound insulating material, and there are, for example, non-woven fabrics and the like.

4. Adhesive

4-1 main agent

The acrylic solvent-based polymer constituting the main agent of the adhesive is formed by polymerizing a (meth)acrylic monomer in a solvent. As the polymer, any one of polymers used in this field can be used. For example: (meth)acrylic acid, itaconic acid, maleic acid (anhydride), fumaric acid (anhydride), crotonic acid and other polymerizable monomers with carboxyl or anhydride groups; (meth)acrylic acid alkyl Esters [methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate ) lauryl acrylate, etc.], mono(meth)acrylates such as 2-hydroxyethyl (meth)acrylate; diethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, etc. Di(meth)acrylate; Tri(meth)acrylate such as pentaerythritol tri(meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide etc. (meth) Homopolymers of monomers in (meth)acrylic monomers such as acrylamide, and multi-polymers such as copolymers and terpolymers composed of two or more. In addition, other than (meth)acrylic monomers such as the aforementioned (meth)acrylic monomers and vinyl acetate, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, styrene, etc. Copolymers of vinyl compounds.

The polymerization initiators used during the polymerization of the above-mentioned monomers specifically include: benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate, neodecyl peroxide Organic peroxide polymerization initiators such as tert-butyl peroxide and 2-ethylhexanoate tert-butyl peroxide; 2,2'-Azobis(2-methylbutyronitrile), 2,2'-Azo Azo-type polymerization initiators such as bicyclohexyl nitrile; radical polymerization initiators such as; the above-mentioned initiators are not particularly limited, and one type may be used alone, or two or more types may be appropriately mixed and used. The usage-amount of a polymerization initiator can be set according to the composition of a monomer composition, reaction conditions, etc., and is not specifically limited.

Moreover, chain transfer agents added during polymerization include, for example: alkyl mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan, and dodecyl mercaptan; octyl thioglycolate, nonyl thioglycolate, Thioglycolic acid esters such as 2-ethylhexyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene, 1-methyl 4-isopropylidene-1-cyclohexene, etc. . Especially when using thioglycolates, 2,4-diphenyl-4-methyl-1-pentene, 1-methyl-4-isopropylidene-1-cyclohexene, the resulting copolymer It has a low odor and is therefore preferred for use. In addition, the amount of the chain transfer agent used can be adjusted in the range of about 0.001 to about 3% by weight of the total monomers polymerized. In addition, the polymerization reaction is usually performed at a temperature of 40 to 100° C. for 2 to 8 hours.

The above-mentioned (meth)acrylic polymer may be composed of one kind, or may be composed of two or more kinds of (meth)acrylic polymers in combination. In addition, other components may be freely added as additives to the above-mentioned (meth)acrylic polymer. Other components are not particularly limited, and various additives may be added in addition to tackifiers, pigments, dyes, diluents, and polymerization inhibitors.

4-2 Crosslinking agent

The crosslinking agent is a substance containing a functional group capable of reacting with the functional group of the above-mentioned (meth)acrylic polymer, that is, a functional group introduced into the molecule by a monomer having a hydroxyl group or a carboxyl group. The bonding agent can further improve the adhesive force and cohesion of the adhesive layer.

The above-mentioned cross-linking agent is not particularly limited as long as it is a compound having a plurality of functional groups capable of reacting with the functional groups of the (meth)acrylic polymer in the molecule. The cross-linking agent is, for example, a multifunctional epoxy Compounds, multifunctional isocyanate compounds, aziridine compounds, and metal crosslinking agents, etc.

As long as the polyfunctional epoxy compound is a compound containing a plurality of epoxy groups in the molecule, it is not particularly limited. The polyfunctional epoxy compound specifically includes: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , 1,6-hexanediol diglycidyl ether, bisphenol A epichlorohydrin type epoxy resin, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3 - bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyltoluidine and the like.

The polyfunctional isocyanate compound is not particularly limited as long as it has a plurality of isocyanate groups in its molecule. The polyfunctional isocyanate compound specifically includes: toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, isophthalic diisocyanate, Diisocyanate compounds such as methyl diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; Biuret polyisocyanate compounds such as N (trade name, manufactured by Sumitomo Bayer Uletan Co., Ltd.), Desmogul IL, Desmogul HL (trade name, manufactured by Bayer A.G. Co., Ltd.), Uroneto EH (trade name, Nippon Polyurethane Industry Co., Ltd. Co., Ltd.) and other polyisocyanate compounds having an isocyanurate ring; Sumijul L (trade name, manufactured by Sumitomo Bayer Uletan Co., Ltd.), Coronet L (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. Adducts of polyisocyanate compounds, etc. In addition, blocked isocyanate compounds in which the isocyanate groups of these polyfunctional isocyanate compounds are made inert by reacting them with a masking agent having active hydrogen can also be used.

Specific examples of aziridine compounds include 2,2'-bishydroxymethylbutanol tris[3-(1-aziridinyl)propionate], 4,4'-bis(ethyleneiminocarbonylamino) Diphenylmethane, etc.

Specific examples of metal crosslinking agents include: coordination of acetylacetone, acetylacetone, acetylacetone, etc. Chelates formed by ligands such as methyl acetate, ethyl acetoacetate, ethyl lactate, and methyl salicylate, etc.

These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used can be determined in consideration of the type of (meth)acrylic polymer and the use of the adhesive composition, etc., and is not particularly limited, but is preferably 0.1 weight parts per 100 parts by weight of the (meth)acrylic polymer 10 parts by weight, more preferably 0.5 parts by weight to 5 parts by weight. Accordingly, since the crosslink density of the (meth)acrylic polymer can be adjusted to an appropriate value, various physical properties of the adhesive composition can be further improved. When the usage-amount of a crosslinking agent is less than 0.1 part by weight, a crosslinking agent may become insufficient, and a crosslinking density may become too low, and cohesive force may become insufficient. In addition, when the amount used is more than 10 parts by weight, the crosslinking density may be too high, the cohesive force may be too high, and the adhesive force and recoil resistance may be lowered. In addition, the method of adding a crosslinking agent to a (meth)acrylic polymer is not specifically limited.

In order to further improve the adhesiveness, it is preferable to mix a tackifier with the main ingredient constituting the adhesive, and the adhesion to adherends such as polyolefin can be improved by adding the tackifier. Tackifiers used in the present invention are, for example, terpene resins, aliphatic petroleum resins, aromatic petroleum resins, coumarone-indene resins, phenolic resins, terpene-phenolic resins, rosin derivatives (rosin, polymerized rosin, Hydrogenated rosin and esters thereof such as glycerin and pentaerythritol, resin acid dimers, etc.), among them, rosin derivatives are preferred, and rosin esters are particularly preferred.

The aforementioned tackifiers may be used alone or in combination of two or more. That is, as a combination of tackifiers, terpene resins and aliphatic petroleum resins, aromatic petroleum resins and coumarone-indene resins, terpene-phenolic resins and rosin derivatives, terpene resins and rosin-derived aliphatic petroleum resins and rosin derivatives, aromatic petroleum resins and rosin derivatives, coumarone-indene resins and rosin derivatives, phenolic resins and rosin derivatives, or rosin derivatives and fatty A mixture of three or more types of petroleum resins and aromatic petroleum resins. In addition, the blending ratio of the tackifier is preferably 1 to 50 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. When it is less than 1 part by weight, the effect of improving the adhesive force and cohesive force is lacking, and on the contrary, when it exceeds 50 parts by weight, the adhesive force and cohesive force will decrease.

4-3. Acetylacetone

Acetylacetone can reduce formaldehyde emission by trapping formaldehyde generated from substances contained in adhesives or skin materials, or formaldehyde generated by heating. It is preferable to add 0.01-2 weight part of acetylacetone with respect to 100 weight part of solid content of the main ingredient containing the said solvent-soluble (meth)acrylic polymer, More preferably, it is 0.05-1 weight part. When it is less than 0.01 parts by weight, the effect of trapping formaldehyde is poor. When it exceeds 2 parts by weight, although the trapping effect is enhanced, it remains as a residual solvent in the automotive interior material after drying, and the cohesive force may be insufficient.

4-4. Other additives

Furthermore, the adhesive may contain various additives such as fillers, pigments, dyes, diluents, anti-aging agents, ultraviolet absorbers, ultraviolet stabilizers, etc., which are compounded in known adhesive compositions, as needed. Only one kind of these additives may be used, or two or more kinds may be used as appropriate. In addition, the additive amount is not particularly limited as long as desired physical properties can be obtained.

4-5. Solvent

Since the solvent of the adhesive does not contain at least toluene substantially, emission of toluene can be prevented. Furthermore, it is preferable not to substantially contain 13 specified by the Ministry of Health, Labor and Welfare's seminar on the problem of sick rooms (indoor air pollution) [intermediate report - 8th to 9th summary (February 8, 2014)]. A volatile organic compound (VOC). The so-called 13 kinds of volatile organic compounds are formaldehyde, toluene, xylene, p-dichlorobenzene, ethylbenzene, styrene, chlorpyrifos, di-n-butyl phthalate, tetradecane, bis(2-ethyl phthalate) Hexyl) esters, diazinon, acetaldehyde, and Fenovocarb.

The type of solvent is not particularly limited, but ester-based or ketone-based solvents are preferred. The ester solvent is not particularly limited, and examples include ethyl acetate, butyl acetate, isobutyl acetate, and the like. The ketone solvent is not particularly limited, and examples thereof include methyl isobutyl ketone, methyl ethyl ketone, acetone, and the like.

4-6. Coating method

The method of applying the adhesive to the base material or the skin material is not particularly limited, and various known methods can be employed. Such methods include, for example, a method of directly applying an adhesive to a base material or a surface material; a method of transferring the applied material to a base material or a surface material after coating an adhesive composition on a release paper wait. Adhesives can be easily applied to substrate or skin materials. There is no particular limitation on the coating equipment used when coating the adhesive on the base material or the skin material, and after the adhesive is coated on the base material or the skin material, by making it dry, the base material or the skin material It is integrated with the adhesive to form an adhesive layer on the surface of the substrate or the skin material (hereinafter referred to as the adhesive surface). The drying temperature is not particularly limited. During drying, for example, the functional group of the (meth)acrylic polymer and the functional group of the crosslinking agent are reacted to form a crosslinked structure. Thereafter, the substrate or the surface material on the side not coated with the adhesive may be superimposed on the adhesive surface of the base material or the surface material on the side coated with the adhesive agent. In addition, before the above-mentioned adhesive agent dries, the base material and the surface material may be pasted together, or the adhesive agent may be applied to both the base material and the surface material.

5. Properties of automotive interior materials

As a result of using the above-mentioned adhesive, when the automotive interior material is heated in water at 90° C. for 2 hours, only 0.05 μg/g or less of formaldehyde is generated.

The effect of the invention

The automobile interior decoration material related to the present invention has excellent effects, and can reduce emission of toluene and formaldehyde.

Description of drawings

Fig. 1 is a front view showing a pillar decorative material according to an embodiment of the present invention.

Fig. 2 is a sectional view taken along line II-II of Fig. 1 .

Fig. 3 is a cross-sectional view of a modified example.

Detailed ways

The present invention provides an interior decoration material for automobiles. The interior decoration material for automobiles is formed by pasting a flexible skin material on a base material made of synthetic resin through an adhesive, wherein the adhesive is Best practice of acrylic solvent-based adhesive comprising a solvent of ester or ketone substantially free of toluene, a main ingredient containing an acrylic polymer soluble in the solvent, a crosslinking agent, and acetylacetone One of the modes is to contain 0.01 to 2 parts by weight of acetylacetone with respect to 100 parts by weight of solid content of the main ingredient.

Next, the present invention will be described using examples. Parts in the examples represent parts by weight, and % represents % by weight.

[Manufacture of pillar decorative materials as interior materials for automobiles]

A cushioning sheet 2 made of foamed synthetic resin forming an inner layer is bonded to the back surface of a fabric 1 forming a surface layer to form a flexible surface material 3 having a two-layer structure. The back surface of the cushioning sheet 2 was coated with an adhesive to a dry weight of 65 g/m ² , and dried at 90° C. for 1 minute to form an adhesive layer 4 . Then, stick the skin material 3 on the surface of the base material 5 of the pillar decoration material obtained by injection molding with synthetic resin, and wrap the edge of the skin material 3 to the back side of the base material 5, so that the adhesive layer 4 The layers are attached on the base material 5 to manufacture the pillar decoration material 10 .

[Measurement method of formaldehyde]

4 mL of distilled water was previously placed in a glass bottle with an internal capacity of 800 to 1000 mL. Put the test piece of pillar decorative material 10 cut into a size of 10 cm x 20 cm into the aforementioned distilled water, and let it stand at a temperature of 90° C. for 2 hours to allow formaldehyde to be absorbed by the distilled water. The concentration of formaldehyde in the test solution was quantified colorimetrically using the acetylacetone method using a photoelectric spectrophotometer or a photoelectric colorimeter.

Example 1

76.9 parts of n-butyl acrylate

20 parts of 2-ethylhexyl acrylate

3 parts acrylic

0.1 parts of 2-hydroxyethyl acrylate

Benzoyl peroxide 0.2 parts

0.05 parts of 1-methyl-4-isopropylidene-1-cyclohexene

85 parts of ethyl acetate

According to the above composition, it was copolymerized under reflux conditions for 3 hours, thereafter, it was copolymerized with unreacted monomers with 0.2 parts of tert-butyl peroxy 2-ethylhexanoate, after the reaction was completed, ethyl acetate 37 parts, cooled to obtain an acrylic copolymer with a non-volatile content concentration of 45%. Furthermore, 20 parts of rosin esters were added to the acrylic copolymer produced above, diluted with 23.5 parts of ethyl acetate, and 1 part of acetylacetone was added to obtain an adhesive having a non-volatile content of 45%. Add 1.5% by weight of Coronet L 45% concentration product to 100 parts by weight of the obtained adhesive, mix, then use the obtained material to manufacture a pillar decorative material by the method described above, measure formaldehyde after heating, and the result 0 μg/g.

Example 2

70 parts of n-butyl acrylate

20 parts of 2-ethylhexyl acrylate

Vinyl acetate 6.9 parts

3 parts acrylic

0.1 parts of 2-hydroxyethyl acrylate

Benzoyl peroxide 0.2 parts

0.05 parts of 1-methyl-4-isopropylidene-1-cyclohexene

85 parts of ethyl acetate

According to the above composition, make it copolymerize under reflux conditions for 3 hours, then use 0.2 parts of tert-butyl peroxy 2-ethylhexanoate to make it copolymerize with unreacted monomers, after the reaction, add ethyl acetate 37 parts, and then cooled to obtain an acrylic copolymer with a non-volatile content concentration of 45%. Furthermore, 20 parts of rosin esters were added to the acrylic copolymer produced above, diluted with 24.3 parts of ethyl acetate, and 0.2 parts of acetylacetone was added to obtain an adhesive composition with a nonvolatile content of 45%. Add 1.5% by weight of Coronet L 45% concentration product to 100 parts by weight of the obtained adhesive, mix, then use the obtained material to manufacture a pillar decorative material by the method described above, measure formaldehyde after heating, and the result 0 μg/g.

Example 3

Except that the addition amount of acetylacetone was reduced to 0.01 part, it was the same as in Example 1 to obtain an adhesive. To 100 parts by weight of the obtained adhesive, add 1.5% by weight of a 45% concentration product of Coronet L, mix, then use the obtained material to manufacture a pillar decorative material by the method described above, measure formaldehyde after heating, The result was 0.3 μg/g.

Comparative example 1

Except not using acetylacetone, other is the same as embodiment 1, obtains adhesive. To 100 parts by weight of the obtained adhesive, add 1.5% by weight of a 45% concentration product of Coronet L, mix, then use the obtained material to manufacture a pillar decorative material by the method described above, measure formaldehyde after heating, The result was 0.4 μg/g.

In addition, this invention is not limited to the said embodiment, As mentioned below, it can change suitably in the range which does not deviate from the essence of this invention.

(1) As shown in Figure 3 (a), through the adhesive layer 4, the skin material 3 consisting only of the fabric 1 is pasted on the base material 5, as shown in Figure 3 (b), through the adhesive layer 4. Paste the skin material 3 consisting only of the cushioning sheet 2 on the base material 5 . In addition, other skin materials listed in the "Summary of the Invention" section were used.

(2) As the surface material, one provided with a sound-insulating material (such as those mentioned in the above method) is used on the back side of the surface layer, and the surface material is bonded to the base material through an adhesive layer.

Claims (2)

1. inner decoration material for vehicle, to have flexual skin material by bond layer sticks on the base material that is made of synthetic resin and forms, it is characterized in that bond layer is formed by the acrylic compounds solvent type adhesive that comprises the solvent that does not contain toluene in fact, the host that contains the acrylic polymer that dissolves in this solvent, crosslinking agent and acetylacetone,2,4-pentanedione.

2. automobile ornament materials as claimed in claim 1 is characterized in that, solid constituent 100 weight portions of host contain acetylacetone,2,4-pentanedione 0.01～2 weight portion relatively.

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