JPH072407B2 - Vinyl chloride resin laminated sheet for vacuum forming to produce matte vacuum formed products - Google Patents

Description

Detailed Description of the Invention

[Industrial field of application] The present invention relates to a vinyl chloride resin sheet for vacuum forming,
In particular, the present invention relates to a vinyl chloride resin sheet for vacuum forming, which does not change the gloss of the sheet after vacuum forming. [Problems to be Solved by Prior Art and Invention] Conventionally, as a polyvinyl chloride resin sheet for vacuum forming,
Sheets using vinyl chloride resin plastisol have been used because of softening of molded products. In order to form a sheet having a squeezing pattern using a vinyl chloride resin plastisol, a vinyl chloride resin plastisol composition is applied to a release paper having an uneven pattern, which is gelled and peeled from the release paper. The resulting vinyl chloride-based resin sheet has a clear transfer of the uneven pattern of the release paper, and the unevenness of the diaphragm can be sufficiently expressed, and is suitable for vehicle interior materials such as automobiles. However, in order to form a matte surface with such a polyvinyl chloride resin sheet for vacuum forming, the surface of the release paper is matted and the glossy state of the release paper is directly transferred to the surface of the vinyl chloride resin sheet. Alternatively, a method of spray coating or gravure coating of a surface treatment agent containing a matting agent has been adopted. The polyvinyl chloride resin sheet for vacuum forming obtained as described above had a matte surface before vacuum forming, but during vacuum forming the matte phenomenon occurred in the stretched part and the surface became glossy. As a result, a vacuum molded product having a matte surface could not be obtained. The polyvinyl chloride-based resin sheet for vacuum forming obtained as described above had a matte surface before vacuum forming. However, when vacuum forming, a matte part and a glossy part are partially formed. It was not possible to obtain a vacuum-formed product having a uniform and matte surface, which was possible. The present invention has been made against such a background of the prior art, and provides a vinyl chloride resin sheet for vacuum forming, which has extremely little glossiness and uneven gloss after vacuum forming. Means for Solving the Problems That is, the present invention provides (1) 1 to 20 parts by weight of a silica-based inorganic matting agent per 100 parts by weight of a vinyl chloride-based resin sheet on the surface of a vinyl chloride-based resin sheet made of a vinyl chloride-based resin plastisol. Parts and / or a vinyl chloride resin laminated sheet for vacuum forming, wherein a vinyl chloride resin layer comprising a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of a crosslinked vinyl chloride resin is formed. (2) A polyurethane resin layer formed of a polyurethane resin solution composition containing 1 to 20 parts by weight of a silica-based inorganic matting agent to 100 parts by weight of a polyurethane resin is formed on the surface of a vinyl chloride resin sheet made of a vinyl chloride resin plastisol. A vinyl chloride resin laminated sheet for vacuum forming which is formed. (3) The vinyl chloride resin sheet for vacuum forming according to any of (1) or (2) above, wherein the vinyl chloride resin sheet made of vinyl chloride resin plastisol is a non-foamed layer. (4) The vinyl chloride resin sheet for vacuum forming according to any one of (1) or (2) above, wherein the vinyl chloride resin sheet made of a vinyl chloride resin plastisol is a foam layer. Is the gist. Examples of the vinyl chloride resin used in the present invention include vinyl chloride alone or vinyl chloride and other vinyl monomers such as vinyl acetate, ethylene, propylene, maleic acid ester, methyl methacrylate, methacrylic acid ester, acrylic acid ester, and higher polymers. Examples thereof include polymers or copolymers obtained by emulsion polymerization or microsuspension polymerization with vinyl ether and the like. These may be used alone or in combination of two or more. Liquid plasticizers that can be used to form plastisols from vinyl chloride-based resins include, for example, phthalic acid di-2-ethylhexyl ester (DOP), phthalic acid diisononyl ester (DINP), phthalic acid butylbenzyl ester (BBP), phthalic acid. General phthalate ester plasticizers such as acid diisodecyl ester (DIDP) and phthalic acid diundecyl ester (DUP), adipic acid dioctyl ester (DOA), sebacic acid dioctyl ester (D
OS), general fatty acid ester plasticizers represented by azelaic acid dioctyl ester (DOZ), trimellitic acid ester plasticizers represented by trimellitic acid trioctyl ester (TOTM), tricresyl phosphate (TCP) ), Triaryl phosphate-based plasticizers such as trixylyl phosphate (TXP),
Epoxy plasticizers such as epoxidized soybean oil,
Polymeric plasticizers such as polyester plasticizers represented by polypropylene adipate and general plasticizers such as chlorinated paraffin can be used, but these plasticizers may be used alone or in combination of two or more. You may use together. These plasticizers are suitable for various intended applications.
It is added in an appropriate amount to the vinyl chloride resin. Generally, the amount added is about 30 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, but the present invention is not limited thereto. As the inorganic matting agent used in the present invention, silica type can be used. The crosslinked vinyl chloride resin used in the present invention means a crosslinked vinyl chloride polymer obtained by polymerizing a vinyl chloride monomer and a polyfunctional monomer or a polyfunctional oligomer. Specific examples of polyfunctional monomers or polyfunctional oligomers to be polymerized with vinyl chloride monomer are diallyl phthalate, diallyl isophthalate, diallyl terephthalate and other diallyl esters of phthalic acid; diallyl maleate, diallyl fumarate, diallyl succinate. , Diallyl itaconate and other ethylenically unsaturated dibasic acid diallyl esters; diallyl adipate, diallyl azelate, diallyl sebacate and other saturated dibasic acid diallyls; diallyl carbinol, diallyl ether and other diallyl compounds , Triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallyl trimellitate and other triallyl compounds, ethylene glycol divinyl ether, n-butanediol divinyl ether Divinyl ethers such as ter and octadecane divinyl ether; divinyl compounds such as divinylbenzene and divinyl sulfone, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimeta Acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, dimethylene glycol diacrylate, dimethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,3-bu Diacryl ester or dimethacryl ester compound of polyhydric alcohol such as lenglycol diacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, triethyl Triacrylic ester or trimethacrylic ester compound of polyhydric alcohol such as methylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, etc. Diallyl ether, bismethacryloyloxyethylene phthalate, 1,3,5-triacryloyl hexa Idro triazine, 2,2-bis (4-acryloxydiethoxyphenyl) propane, etc. polyfunctional monomer,
1,2-polybutadiene, epoxidized 1,2-polybutadiene,
Examples thereof include polyfunctional oligomers such as acrylate-modified polybutadiene, epoxy acrylate prepolymer, oligoester acrylate prepolymer, urethane acrylate prepolymer, spiroacetal acrylate prepolymer, and bisphenol A modified acrylate prepolymer. Further, the vinyl chloride resin of the present invention, as a stabilizer,
For example, metal stearate such as lead stearate, barium stearate, zinc stearate, cadmium stearate, calcium stearate, tin-based stabilizer such as dibutyltin dilaurate, dibutyltin malate, organotin mercaptide, organotin sulfonamide, tribasic Lead sulfate, tribasic lead phosphite, tribasic lead maleate and the like are used, and these stabilizers can be used alone or in combination of two or more, and the stabilizer is not particularly limited. The amount of the stabilizer added is 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Further, the vinyl chloride resin sheet can be made into a foamed sheet by adding a foaming agent. In the case of forming a foamed sheet, for example, azodicarbonamide, dinitrosopentatetramine, oxybisbenzenehydrazide, which is a foaming agent for vinyl chloride-based resin, can be used as a foaming agent, and foaming can be performed as necessary. Agents or foam suppressors may be added. Other than the above, if necessary, antimony trioxide, flame retardant such as trialkoxyalkyl phosphate, calcium carbonate, magnesium carbonate, in addition to fillers such as aluminum hydroxide, processing aids, pigments, ultraviolet absorbers, Antistatic agents, antiaging agents, etc. can also be added. Of course, compounds other than those exemplified here can be added. In the present invention, on the surface of a vinyl chloride resin sheet made of vinyl chloride resin plastisol, 1 to 20 parts by weight of an inorganic matting agent or 5 to 100 parts by weight of a crosslinked vinyl chloride resin based on 100 parts by weight of the vinyl chloride resin. Silica-based inorganic matting agent 1 to 100 parts by weight of vinyl chloride-based resin layer or polyurethane resin containing vinyl chloride-based resin composition containing
It is sufficient that the polyurethane resin layer containing 20 to 20 parts by weight is formed, and the vinyl chloride resin sheet may be a single layer or a multi-layer. In the case of multiple layers, it may be either a non-foamed layer or a foamed layer or a combination of a non-foamed layer and a foamed layer. As the polyurethane resin used in the present invention, any polyurethane resin generally used for producing synthetic leather can be used. As a specific example,
Polyether polyurethane containing polytetramethylene glycol or polypropylene glycol as a polyol component, polyester polyurethane containing a polyester obtained by reacting a hydroxyl compound having 4 or more carbon atoms with a dibasic acid as a polyol component, ε-caprolactone polyester Examples thereof include a polyester-based polyurethane having a polyol component as a polyol component and a polycarbonate-based polyurethane having a polycarbonate component as a polyol component. From the viewpoint of hydrolysis resistance and the like, a polyurethane resin containing 50% or more of a polycarbonate-based polyurethane is preferable. The polycarbonate-based polyurethane resin has the general formula (However, R = − (CH ₂ ) p− and P ≧ 2.
N = 5 to 200), a polyalkylene polycarbonate-based polyol such as 1,6-hexane polycarbonate polyol, or a mixed polyol and isocyanate in which a part of the polyalkylene polycarbonate-based polyol is replaced with a polyoxyalkylene-modified polycarbonate. Polymers with chain extenders can be used. As the isocyanate, tetramethylene diisocyanate, 1,6-hexane diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 3,3'-dimethyl-4,
4'-diisocyanate dicyclohexylmethane, 4,4 '
-Alphatic or alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, aromatic diisocyanates such as xylylene diisocyanate can be used, but aliphatic or alicyclic diisocyanates or hydrogenated Polycarbonate polyurethane using diphenylmethane diisocyanate is non-yellowing type,
Particularly preferred. The vacuum-molding vinyl chloride resin laminated sheet of the present invention comprises 1 to 20 parts by weight of a silica-based inorganic delusterant or a cross-linked vinyl chloride resin on 100 parts by weight of the vinyl chloride resin on the surface of a release carrier such as release paper. Vinyl chloride resin plastisol composition or polyurethane resin 100 containing 5 to 100 parts by weight
A polyurethane resin solution composition containing 1 to 20 parts by weight of a silica-based inorganic matting agent is applied to parts by weight by a commonly used coating method such as a doctor knife coating method, a roll coating method, or a screen printing method. Is heated, then a general vinyl chloride resin plastisol composition is overlaid and heated, and then the releasable carrier is peeled off. A diaphragm can be formed on the surface of the vacuum-molding vinyl chloride resin laminated sheet, and the diaphragm is formed by using the mold having the diaphragm formed on the surface of the releasable carrier.
By transferring this diaphragm to the surface of the sheet during sheet molding, the diaphragm may be formed at the same time as the sheet is molded, or may be formed by a post-embossing method in which the diaphragm is formed after forming the sheet. Moreover, the vinyl chloride resin laminated sheet for vacuum forming of the present invention may be laminated with a stretchable raw cloth such as Woolly nylon or Woolly Tetron on the back surface thereof. Furthermore, a surface treatment agent such as a vinyl chloride resin-based, acrylic resin-based, or polyurethane-based surface treatment agent can be applied to the surface of the vinyl chloride-based resin layer in order to adjust the surface feel and gloss. [Operation] In the present invention, the vinyl chloride resin laminated sheet for vacuum forming is composed of a vinyl chloride resin plastisol composition, and 100 parts by weight of the vinyl chloride resin is added to the surface of the vinyl chloride resin sheet of the silica inorganic inorganic matting agent. To 20 parts by weight or 5 to 100 parts by weight of crosslinked vinyl chloride resin, 1 to 20 parts by weight of a silica-based inorganic matting agent per 100 parts by weight of a vinyl chloride resin layer or polyurethane resin comprising a vinyl chloride resin plastisol composition. Since a polyurethane resin layer composed of a polyurethane resin solution composition containing a part is formed, it does not cause luster and uneven gloss due to vacuum forming like a conventional vinyl chloride resin sheet for vacuum forming. Inner panels, safety pads, lids, console boxes used for interiors of vehicles such as automobiles and vehicles such as ships It is suitable to assist grip and the like. [Examples] Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited to these examples. Example 1 A vinyl chloride resin plastisol of Formulation Example 4 shown in Table 1 was kneaded for 20 minutes by a liquor machine, and then applied to a release paper having a leather diaphragm-like uneven pattern so as to have a thickness of 0.1 mm. In 2
After heating for a minute, add the vinyl chloride resin plastisol of Formulation Example 1
It was applied to a thickness of 0.4 mm and heated at 200 ° C. for 2 minutes to obtain a vinyl chloride resin laminated sheet for vacuum forming. The obtained vinyl chloride resin laminated sheet had the uneven pattern formed on the release paper clearly transferred, and had a matte surface and a good leather-like appearance. This vinyl chloride resin laminated sheet for vacuum forming is heated with a far infrared heater,
When vacuum forming was performed at a surface temperature of 160 ° C, a good vacuum formed product was obtained. With respect to the obtained vacuum-formed product, the gloss change was visually observed in comparison with the vinyl chloride resin laminated sheet before vacuum forming, and evaluated according to the following criteria. The results are shown in Table 2.

[Standard of gloss change]

⊙: Almost no gloss change and no uneven gloss compared to the sheet before vacuum forming. ◯: A slight gloss change is seen compared to the sheet before vacuum forming, but it has a matte appearance and has extremely little uneven gloss. X: A change in gloss is clearly seen or uneven gloss is clearly seen as compared with the sheet before vacuum forming. Examples 2 to 4 Vinyl chloride resin laminated sheets were obtained in the same manner as in Example 1 except that the vinyl chloride resin plastisols of Formulation Examples 5 to 7 were used instead of the vinyl chloride resin plastisol of Formulation Example 4. The same test as in Example 1 was performed on each of the obtained vacuum-molded vinyl chloride resin laminated sheets. The results are shown in Table 2. Example 5 A polyurethane paper solution composition of Formulation Example 8 (using 1,6-hexane polycarbonate polyurethane as a polyurethane resin) was applied to a release paper having a leather squeeze-shaped concavo-convex pattern so as to have a dry thickness of 20 μm, After heating and drying this, the vinyl chloride resin plastisol of Formulation Example 1 was applied to a thickness of 0.4 mm and heated at 200 ° C. for 2 minutes to obtain a vinyl chloride resin laminated sheet for vacuum forming. The vinyl chloride resin laminated sheet for vacuum forming thus obtained was tested in the same manner as in Example 1. The results are shown in Table 2. Examples 6 to 7 The vinyl chloride resin plastisols of Formulation Examples 1, 2, 3 and 4 were used, and the combination of Formulation Example 1 and Formulation Example 2 and Formulation Example 4 and Formulation Example 2 and Formulation Example 3 and Formulation Example 4 were used. 0.1m surface layer on release paper
It was applied to a thickness of m and heated at 200 ° C. for 2 minutes, and then applied so that the upper layer of the coating layer had a thickness of 0.2 mm on the surface layer and heated at 200 ° C. for 2 minutes. After that, the lower layer of the coating layer was applied so as to have a thickness of 0.2 mm, heated at 200 ° C. for 2 minutes and then foamed to obtain a vinyl chloride resin laminated sheet for vacuum forming. The vinyl chloride resin laminated sheet for vacuum forming thus obtained was tested in the same manner as in Example 1. The results are shown in Table 2. Example 8 A combination of the combination example 2 and the combination example 4 provided a surface layer of 0.
Apply to a thickness of 1 mm, heat this at 200 ° C for 2 minutes, then apply a coating layer of 0.4 mm thickness on the surface layer, heat this at 200 ° C for 2 minutes, and then foam. Thus, a vinyl chloride resin laminated sheet for vacuum forming was obtained. The vinyl chloride resin laminated sheet for vacuum forming thus obtained was tested in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 1 The vinyl chloride resin plastisol of Formulation Example 1 shown in Table 1 was kneaded for 20 minutes with a Likai machine, and then applied to a release paper having a leather diaphragm-like uneven pattern to a thickness of 0.5 mm, and this was applied at 200 ° C. In 2
After heating for 15 minutes, the release paper is peeled off, and a surface treatment agent consisting of an acrylic resin solvent solution containing 5 parts by weight of talc is applied on the peeled surface by a gravure printing method to a thickness of 15 μm and laminated with vinyl chloride resin for vacuum forming. Got the sheet. Example 1 of the obtained vinyl chloride resin laminated sheet for vacuum forming
The same test was performed. The results are shown in Table 2. Comparative Example 2 A combination of Formulation Example 2 and Formulation Example 1 was applied to a release paper having a matte tone leather-like uneven pattern so that the surface layer had a thickness of 0.1 mm, and this was applied at 200 ° C. for 2 minutes. After heating, apply a coating layer on the surface layer to a thickness of 0.4 mm.
After heating at 0 ° C. for 2 minutes, foaming was performed to obtain a vinyl chloride resin laminated sheet for vacuum forming. The vinyl chloride resin laminated sheet for vacuum forming thus obtained was tested in the same manner as in Example 1. The results are shown in Table 2. As is clear from Table 2, the vinyl chloride resin laminated sheet for vacuum forming of the present invention has a silica-based inorganic luster for 100 parts by weight of the vinyl chloride resin on the surface of the vinyl chloride resin sheet made of the vinyl chloride resin plastisol composition. 1 to 20 parts by weight of a vinyl chloride resin or 5 to 100 parts by weight of a crosslinked vinyl chloride resin or a vinyl chloride resin layer made of a plastisol composition of vinyl chloride resin or 100 parts by weight of a polyurethane resin to 1 part of a silica-based inorganic matting agent Since a polyurethane resin layer composed of a polyurethane resin solution composition containing up to 20 parts by weight is formed, glossiness and gloss unevenness are generated by vacuum forming like a conventional vinyl chloride resin sheet for vacuum forming. It can be seen that this is extremely rare (Examples 1 to 8). On the other hand, a vinyl chloride resin sheet for vacuum forming (Comparative Example 1) manufactured by a method of spray coating or gravure coating a surface treatment agent containing a matting agent on the surface of the vinyl chloride resin sheet, and release paper. The vinyl chloride resin sheet for vacuum forming (comparative example 2), in which the surface is matte and the glossy state of the release paper is directly transferred to the surface of the vinyl chloride resin sheet (Comparative Example 2), causes a clear gloss unevenness on the sheet surface when vacuum forming. It can be seen that the matte state before vacuum forming cannot be maintained due to glossiness. [Effects of the Invention] The present invention is such that the polyvinyl chloride-based resin sheet for vacuum forming is a silica-based inorganic based on 100 parts by weight of the vinyl chloride-based resin sheet on the surface of the vinyl chloride-based resin sheet made of the vinyl chloride-based resin plastisol composition. Matting agent 1 to 20 parts by weight or 5 to 100 parts by weight of cross-linked vinyl chloride resin, vinyl chloride resin layer composed of vinyl chloride resin plastisol composition or 100 parts by weight of polyurethane resin to silica-based inorganic matting agent Since the polyurethane resin layer composed of the polyurethane resin solution composition containing 1 to 20 parts by weight is formed, the glossiness and gloss unevenness can be obtained by vacuum forming like the conventional vinyl chloride resin sheet for vacuum forming. Inner panels, safety pads, lids, consoles that are used for interiors of vehicles such as automobiles and vehicles such as ships without generating Box, it is suitable to assist grip and the like.

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Claims (4)

[Claims] 1. A vinyl chloride resin sheet composed of a vinyl chloride resin plastisol, 1 to 20 parts by weight of a silica-based inorganic matting agent and / or 5 to 100 parts of a crosslinked vinyl chloride resin on 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin laminated sheet for vacuum forming, wherein a vinyl chloride resin layer comprising a vinyl chloride resin plastisol composition containing parts by weight is formed. 2. A polyurethane resin layer comprising a polyurethane resin solution composition containing 1 to 20 parts by weight of a silica-based inorganic matting agent per 100 parts by weight of a polyurethane resin on the surface of a vinyl chloride resin sheet made of a vinyl chloride resin plastisol. A vinyl chloride resin sheet for vacuum forming, in which a sheet is formed. 3. The vacuum molding vinyl chloride resin sheet according to claim 1, wherein the vinyl chloride resin sheet made of a vinyl chloride resin plastisol is a non-foaming layer. 4. The vinyl chloride resin sheet made of a vinyl chloride resin plastisol is a foam layer.
The vinyl chloride resin sheet for vacuum forming according to any one of 1.