JPH03224733A - Vinyl chloride resin laminated sheet for vacuum molding for manufacture of frosted vacuum molded product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

[Industrial Application Field] 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 that does not change the gloss of the sheet after vacuum forming. [Prior art and problems to be solved by the invention] Conventionally, as a polyvinyl chloride resin sheet for vacuum forming,
Sheets using vinyl chloride resin plastisol have been used to make molded products softer. In order to form a sheet with a squeeze pattern using a vinyl chloride resin plastisol, a vinyl chloride resin plastisol composition is applied to a release paper having an uneven pattern, and this is gelled and peeled off from the release paper. The uneven pattern of the release paper is clearly transferred to the resulting vinyl chloride resin sheet, and the unevenness of the aperture, even minute ones, can be sufficiently expressed, making it suitable for interior materials for vehicles such as automobiles. However, in order to form a matte surface on such a polyvinyl chloride resin sheet for vacuum forming, it is necessary to make the surface of the release paper matte and transfer the glossy state of the release paper as is to the surface of the vinyl chloride resin sheet. The method used was to spray paint or gravure coat a surface treatment agent containing a cape agent. The vacuum-formed polyvinyl chloride resin sheet obtained as in step (2) had a matte surface before vacuum forming, but a phenomenon of stripping occurred in the elongated areas of the vacuum forming, and the surface became glossy. As a result, a vacuum-formed product with a matte surface could not be obtained. In addition, the vacuum-formed polyvinyl chloride resin sheet obtained as in (■) had a matte surface before vacuum forming, but after vacuum forming, some parts were matte and others were glossy. This resulted in uneven gloss, making it impossible to obtain a vacuum-formed product with a uniform matte surface. The present invention was made against the background of such conventional technology, and provides a vinyl chloride resin sheet for vacuum forming that has extremely little matting or unevenness after vacuum forming. (Means for Solving the Problems) That is, the present invention provides the following: (1) 1 to 20 parts by weight of an inorganic matting agent and A vinyl chloride resin laminate sheet for vacuum forming, on which a vinyl chloride resin layer is formed from a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of a crosslinked vinyl chloride resin. (2) Vinyl chloride resin layer Vinyl chloride for vacuum forming, in which a polyurethane resin layer made of a polyurethane resin solution composition containing 1 to 20 parts by weight of an inorganic matting agent per 100 parts by weight of polyurethane resin is formed on the surface of a vinyl chloride resin sheet made of resin plastisol. (3) The vinyl chloride resin sheet for vacuum forming according to claim 1 or 2, wherein the vinyl chloride resin sheet made of vinyl chloride resin plastisol is a non-foaming layer. (4) Chlorinated The vinyl chloride resin sheet for vacuum forming according to claim 1 or 2, wherein the vinyl chloride resin sheet made of vinyl resin plastisol is a foam layer. Vinyl resins include vinyl chloride alone, vinyl chloride and other vinyl compounds such as evaporated vinyl acetate, ethylene, propylene, maleic ester, methyl methacrylate, methacrylic ester, acrylic ester, and higher vinyl ether. Examples include polymers or copolymers obtained by emulsion polymerization or microsuspension polymerization, and these may be used alone or in combination. Plastisol is formed from vinyl chloride resin. Examples of liquid plasticizers that can be used include Phthal 11-2-
Ethylhexyl ester (DOP), diisononyl phthalate (DINP), butyl benzyl phthalate (BBP), diisodecyl phthalate (D
General phthalate ester plasticizers such as IDP), diundecyl phthalate (DUP), dioctyl adipate (DOA), dioctyl sebacate (DO3), and dioctyl azelaate (DOZ) Trioctyl trimellitate (TO
trimellitic acid ester plasticizers represented by TM),
In addition to triaryl phosphate plasticizers such as tricresyl phosphate (TCP) and lyxylyl phosphate (TXP), epoxy plasticizers such as epoxidized soybean oil, polypropylene adipate, etc. Polymer plasticizers such as polyester plasticizers, such as polyester plasticizers, 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 also use it. These plasticizers can be used for various purposes,
An appropriate amount is added to the vinyl chloride resin. Generally, the amount added is about 30 to 100 parts by weight per 100 parts by weight of the vinyl chloride resin, but the present invention is not limited to this. As the mw-free eraser used in the present invention, silica-based, talc-based, feldspar, etc. can be used. Further, the crosslinked vinyl chloride resin used in the present invention refers to a crosslinked vinyl chloride polymer obtained by polymerizing a vinyl chloride monomer and a polyfunctional monomer or polyfunctional oligomer. Specific examples of polyfunctional monomers or polyfunctional oligomers to be polymerized with vinyl chloride vinyl monomers include diallyl esters of phthalic acid such as diallyl phthalate, diallyl isophthalate, and diallyl terephthalate; diallyl maleate, diallyl fumarate, and diallyl. Diallyl esters of ethylenically unsaturated dibasic acids such as succinate and diallylitaconate; diallyl esters of saturated dibasic acids such as diallyl adipate, diallyl azelate and diallyl sebacate; diallyl such as diallyl carbinol and diallyl ether compounds, triallyl compounds such as triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallyl trimellitate, divinyl ethers such as ethylene glycol divinyl ether, n-butanediol divinyl ether, octadecane divinyl ether; divinylbenzene ,
Divinyl compounds such as divinyl sulfone, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate , dimethylene glycol diacrylate, dimethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate,
Diacrylic polyhydric alcohols such as polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1.3-butylene glycol diacrylate, 1.3-butylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, etc. Ester or dimethacrylic ester compounds, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, etc. In addition to triacrylic ester or trimethacrylic ester compounds of alcohols, polypropylene glycol diallyl ether, bismethacryloyloxyethylene phthalate, 1.3.5
-) lyacryloylhexahydrotriazine, 2.
Polyfunctional monomers such as 2-bis(4-acryloxyjethoxyphenyl)propane, 1,2-polybutadiene,
Multifunctional oligomers such as epoxidized 1.2-polybutadiene, acrylate-modified polybutadiene, epoxy acrylate prepolymers, oligoester acrylate prepolymers, urethane acrylate prepolymers, spiroacecool acrylate prepolymers, and bisphenol A-modified acrylate prepolymers. can be mentioned. In addition, the vinyl chloride resin of the present invention includes, as a stabilizer,
For example, metal soaps such as lead stearate, barium stearate, zinc stearate, cadmium stearate, and calcium stearate, tin-based stabilizers such as dibutyltin dilaurate, dibutyltin malate, tin mercaptide, organotin sulfonamide, and tribasic. Stabilizers such as tribasic lead sulfate, tribasic lead phosphite, and tribasic lead maleate are used, and these stabilizers can be used alone or in combination of two or more, and there are no particular restrictions on the stabilizers. The amount of the stabilizer added is about 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight, per 100 parts by weight of the vinyl chloride resin. In addition, this vinyl chloride resin sheet can be made into a foam sheet by adding a blowing agent. When making a zero foam sheet, the foaming agent may be, for example, azodicarbonamide, dinitrosopentamide, which is a foaming agent for vinyl chloride resin. Foaming can be achieved by using tetramine, oxybisbenzene hydrazide, etc., and a foaming accelerator or foaming inhibitor may be added as necessary. In addition to the above, flame retardants such as antimony dioxide and trialkoxyalkyl phosphate, fillers such as calcium carbonate, magnesium carbonate, and aluminum hydroxide, processing aids, pigments, ultraviolet absorbers, and electrostatic charges may be added as necessary. Inhibitors, anti-aging agents, etc. can also be added. Of course, compounds other than those exemplified here can also 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 is added to 100 parts by weight of the vinyl chloride resin. 1 part by weight of an inorganic matting agent per 100 parts by weight of a vinyl chloride resin layer or polyurethane resin made of a vinyl chloride resin composition containing
It is sufficient that a polyurethane resin layer containing up to 20 parts by weight is formed, and the vinyl chloride resin sheet may be a single layer or a multilayer. In the case of multiple layers, it may be a combination of non-foamed layers, foamed layers, or a combination of a non-foamed layer and a foamed layer. As the polyurethane resin used in the present invention, any polyurethane resin used in -i to produce synthetic leather can be used. As a specific example,
Polyether polyurethane containing polytetramethylene glycol or polypropylene glycol as a polyol component, polyester polyurethane containing polyester obtained by reacting a hydroxyl compound having 4 or more carbon atoms with a dibasic acid as a polyol component, e-caprolactone polyester Examples include polyester polyurethane containing polyester as a polyol component, polycarbonate polyurethane containing polycarbonate as a polyol component, etc., but polyurethane resins containing 50% or more of polycarbonate polyurethane are preferred from the viewpoint of hydrolysis resistance. As the polycarbonate-based polyurethane resin, a polyalkylene polycarbonate-based polyol represented by the general formula (where R=-(CH,)p- and P≧2, and n=5 to 200), for example, 1.6 -Hexane polycarbonate polyol or the like, or a polymer of a mixed polyol obtained by substituting a part of the polyalkylene polycarbonate polyol with polyoxyalkylene-modified polycarbonate, an isocyanate, and a chain extender can be used. As the isocyanate, tetramethylene diisocyanate, 1.6-hexane diisocyanate, 2.2.4
-) trimethyl-1,6-hexane diisocyanate,
■-Methylcyclohexane-2,4-diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, aliphatic or alicyclic diisocyanates such as dicyclohexylmethane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, diphenylmethane Aromatic diisocyanates such as diisocyanate, hydrogenated diphenylmethane diisocyanate, and xylylene diisocyanate can be used, but polycarbonate polyurethanes using aliphatic or alicyclic diisocyanates and hydrogenated diphenylmethane diisocyanate are non-yellowing types and are particularly preferred. . The vinyl chloride resin laminated sheet for vacuum forming of the present invention is coated with 1 to 20 parts by weight of an inorganic matting agent or 5 to 5 parts by weight of a crosslinked vinyl chloride resin per 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 containing 100 parts by weight or polyurethane resin 100 parts by weight
A polyurethane resin solution composition containing 1 to 20 parts by weight of an inorganic matting agent is applied by a commonly used coating method such as a doctor knife coating method, a roll coating method, or a screen printing method, and then heated. After that, a general vinyl chloride resin plastisol composition is layered and heated, and then the release agent is peeled off. Restrictions can be formed on the surface of this vinyl chloride resin laminated sheet for vacuum forming.
By using a releasable carrier with a restriction formed on the surface and transferring the restriction to the sheet surface during sheet forming, the restriction may be formed at the same time as the sheet is formed, or after the sheet is formed. It may be formed by an embossing method after forming the diaphragm using an embossing roll. Further, the vinyl chloride resin laminated sheet for vacuum forming of the present invention may be formed by laminating a stretchable cloth such as woolly nylon or woolly tetron on the back side thereof. Furthermore, a surface treatment agent such as a vinyl chloride resin, an acrylic resin, or a polyurethane may be applied to the surface of the vinyl chloride resin layer in order to adjust the surface feel. [Function] In the present invention, the vinyl chloride resin laminated sheet for vacuum forming is coated with an inorganic matting agent l to 100% of the vinyl chloride resin on the surface of the vinyl chloride resin sheet made of a vinyl chloride resin plastisol composition. 1 part of a vinyl chloride resin layer made of a vinyl chloride resin plastisol composition containing 20 parts or 5 to 100 parts of a cross-linked vinyl chloride resin or 1 part of a polyurethane resin without a quenching agent
Since a polyurethane resin layer is formed from a polyurethane resin solution composition containing ~20 parts by weight, vacuum forming may cause matting or uneven luster, unlike conventional vacuum forming vinyl chloride resin sheets. without doing,
It is suitable for inner panels, safety panels, lids, console boxes, assist grips, etc. used in the interior of vehicles such as automobiles and vehicles such as ships. [Examples] Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples. Example 1 After kneading the vinyl chloride resin plastisol of Formulation Example 4 shown in Table 1 for 20 minutes in a Raikai machine, it was applied to a release paper having a leather-like uneven pattern to a thickness of 0.1aII11. After heating at °C for 2 minutes, the vinyl chloride resin plastisol of Formulation Example 1 was applied to a thickness of 0.4 cm and heated at 200'C for 2 minutes to obtain a vinyl chloride resin laminate 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 good appearance of leather scraps with a matte surface. When this vacuum-forming vinyl chloride resin laminated sheet was heated with a far-infrared heater and vacuum-formed at a surface temperature of 160°C, a good vacuum-formed product was obtained. The resulting vacuum-formed product was visually observed for changes in gloss in comparison with the vinyl chloride resin laminate sheet before vacuum-forming, and evaluated using the following criteria. The results are shown in Table 2.

[Standards for gloss change]

◎...Compared to the sheet before vacuum forming, there is almost no change in gloss, and there is no unevenness at all. O: There is a slight change in gloss compared to the sheet before vacuum forming, but it has a matte appearance, and there is very little unevenness in gloss. ×: A change in gloss is clearly seen compared to the sheet before vacuum forming, or unevenness is clearly observed. Examples 2 to 4 Vinyl chloride resin laminate 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 in place of the vinyl chloride resin plastisol of Formulation Example 4. The same tests as in Example 1 were conducted on each of the obtained vacuum-forming vinyl chloride resin laminate sheets. The results are shown in Table 2. Example 5 The polyurethane resin solution composition of Blend Example 8 (1.6
- Hexane polycarbonate-based polyurethane) was applied to a dry thickness of 20 μm, and after drying by heating, 0.0 μm of vinyl chloride resin plastisol of Formulation Example 1 was applied.
It was coated to a thickness of 4+m+m and heated at 200°C for 2 minutes to obtain a vinyl chloride resin laminate sheet for vacuum forming. The same tests as in Example 1 were conducted on the obtained vinyl chloride resin laminate sheet for vacuum forming. The results are shown in Table 2. Examples 6 to 7 Using the vinyl chloride resin plastisol of Formulation Example 1.2.3.4, combinations of Formulation Example 1, Formulation Example 2, Formulation Example 4, Formulation Example 2, Formulation Example 3, and Formulation Example 4 were used. The surface layer on the release paper is 0.
After applying the coating to a thickness of 1 mm and heating it at 200°C for 2 minutes, the upper layer of the film layer becomes 0.2+ on the surface layer.
Apply it to a thickness of am and heat it at 200°C for 2 hours.
After heating for minutes, the lower layer of the film layer was coated to a thickness of 0.2 mm, heated at 200°C for 2 minutes, and foamed to obtain a vinyl chloride resin laminate sheet for vacuum forming. The same tests as in Example 1 were conducted on the obtained vinyl chloride resin laminate sheet for vacuum forming. The results are shown in Table 2. Example 8 The combination of Formulation Example 2 and Formulation Example 4 resulted in no surface layer on the release paper.
．． Apply it to a thickness of 11III11 and apply it to a thickness of 2
After heating at 00°C for 2 minutes, a film layer of 0.0°C was formed on the surface layer.
It was coated to a thickness of 4 mm, heated at 200°C for 2 minutes, and then foamed to obtain a vinyl chloride resin laminate sheet for vacuum forming. The same test as in Example 1 was conducted on the obtained 81-layer sheet of vinyl chloride resin for vacuum forming. The results are shown in Table 2. Comparative Example 1 After kneading the vinyl chloride resin plastisol of Formulation Example 1 shown in Table 1 for 20 minutes in a Laikai machine, it was applied to a release paper having a leather-like uneven pattern to a thickness of 0.5 an.
After heating at 00°C for 2 minutes, the release paper was peeled off, and a surface treatment agent made of an acrylic resin solvent solution containing 5 parts by weight of talc was applied to the peeled surface using a gravure printing method to a thickness of 15 μm, followed by vacuum forming. An 81-layer sheet of vinyl chloride resin was obtained. The same tests as in Example 1 were conducted on the obtained vinyl chloride resin laminate sheet for vacuum forming. The results are shown in Table 2. Comparative Example 2 A combination of Formulation Example 2 and Formulation Example 1 was coated on release paper having a matte finish and a leather-like uneven pattern so that the surface layer had a thickness of 0.1111 mm, and this was heated at 200°C. After heating for 2 minutes, a film layer was applied on the surface layer to a thickness of 0.411II11, and this was heated at 200°C for 2 minutes and then foamed to obtain a vinyl chloride resin laminate sheet for vacuum forming. . The same tests as in Example 1 were conducted on the obtained vinyl chloride resin laminate sheet for vacuum forming. The results are shown in Table 2. (The following is a blank space) As is clear from Table 2, the vinyl chloride resin laminate sheet for vacuum forming of the present invention has a vinyl chloride resin sheet made of a vinyl chloride resin plastisol composition with 100% vinyl chloride resin on the surface of the vinyl chloride resin sheet. No 41Ii2. Disinfectant 1-2
A vinyl chloride resin layer or a polyurethane resin layer consisting of a vinyl chloride resin plastisol composition containing 0 parts by weight or 5 to 100 parts by weight of a crosslinked vinyl chloride resin
Since the polyurethane resin layer is formed from a polyurethane resin solution composition containing 1 to 20 parts by weight of a non-1a dissipating agent, it is similar to conventional vacuum forming vinyl chloride resin sheets. It can be seen that the occurrence of deglossing and uneven gloss due to vacuum forming is extremely rare (Examples 1 to 8). On the other hand, on the surface of the vinyl chloride resin sheet,
A vinyl chloride resin sheet for vacuum forming (Comparative Example 1) manufactured by spray painting or gravure coating with a surface treatment agent containing a capping agent, and A vinyl chloride resin sheet for vacuum forming (comparative example 2) in which the state was directly transferred to the surface of the vinyl chloride resin sheet (comparative example 2) produced clear unevenness on the sheet surface and lost its luster when vacuum forming. It can be seen that the matte state cannot be maintained. [Effects of the Invention] As described above, the present invention provides a polyvinyl chloride resin sheet for vacuum forming that contains 100% vinyl chloride resin on the surface of a vinyl chloride resin sheet made of a vinyl chloride resin plastisol composition.
A vinyl chloride resin layer consisting of a vinyl chloride resin plastisol composition containing 1 to 20 parts by weight of an inorganic matting agent or 5 to 100 parts by weight of a crosslinked vinyl chloride resin or an inorganic matting agent per 100 parts by weight of a polyurethane resin. Since the polyurethane resin layer is formed from a polyurethane resin solution composition containing 1 to 20 parts by weight of a matting agent, it cannot be matted or matted by vacuum forming like conventional vacuum forming vinyl chloride resin sheets. It does not cause uneven gloss and is suitable for inner panels, safety bands, lint, console revo-nx, assist grips, etc. used for the interior of vehicles such as automobiles and vehicles such as ships.

Claims (4)

[Claims] (1) The surface of a vinyl chloride resin sheet made of vinyl chloride resin plastisol contains 1 to 20 parts by weight of an inorganic matting agent and/or 5 to 100 parts by weight of a crosslinked vinyl chloride resin per 100 parts by weight of vinyl chloride resin. A vinyl chloride resin laminate sheet for vacuum forming, on which a vinyl chloride resin layer is formed from a vinyl chloride resin plastisol composition. (2) A polyurethane resin layer made of a polyurethane resin solution composition containing 1 to 20 parts by weight of an inorganic matting agent per 100 parts by weight of polyurethane resin is formed on the surface of a vinyl chloride resin sheet made of vinyl chloride resin plastisol. PVC resin laminated sheet for vacuum forming. (3) The vinyl chloride resin sheet for vacuum forming according to claim 1 or 2, 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 claim 1 or 2, wherein the vinyl chloride resin sheet made of vinyl chloride resin plastisol is a foam layer.