JPS6025750A - Manufacture of synthetic resin composite sheet - 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 (Technical Field) The present invention relates to a method for producing a synthetic resin composite sheet using an electron beam.

(Prior Art) Conventionally, the following two methods can be exemplified as methods for manufacturing this type of composite sheet.

The / is a plate-shaped base material coated with radiation-cured forest material, overlaid with an endless belt with an uneven pattern, and by irradiating it with radiation in this state, the coating film is cured while forming unevenness on the coated surface. After curing, the endless belt is peeled off (Japanese Patent Application Laid-open Akihiro?-1'591I).
No. 4).

Another method is to apply an electron beam curable liquid material to a mold material having irregularities, then laminate a substrate on the coated surface, harden it with an electron beam, and then remove the mold material.

However, all of the above methods are good when the substrate is non-permeable, but when it is permeable (the coating material soaks into the substrate, the back side becomes resinous, or the uneven surface of the product This results in the disadvantage that a part of the base material is exposed, and it also becomes difficult to accurately form unevenness.

(Object of the invention) The object of the present invention is to provide a method for manufacturing a synthetic resin composite sheet that does not eliminate M, which is a disadvantage of the above-mentioned prior art, and does not impair the texture of the base material, and can accurately form unevenness. shall be.

(Structure of the Invention) In the present invention, an electron beam curable composition having a viscosity of lθ000 c, p, g or more at room temperature is applied to a mold material on which an uneven pattern has been formed in advance, and then a permeable base material is applied to the modified surface. Laminate 1-
The gist of the method is to irradiate the entire surface with an electron beam, and then peel off the cured product integrated with the base material from the mold material.

FIG. 1 is a conceptual diagram for explaining the invention in detail, in which an electron beam curable composition is coated on the uneven surface of the mold side using a hot melt coating device 3, and a permeable substrate is coated with the electron beam curable composition. After laminating, the electronic section irradiation device bVc is applied.
The electron beam curable composition is cured by irradiation with an electron beam to form a cured product 7, and finally, the mold material/glass permeable base material and the cured film 7 are removed from the mold.

As the mold side l, a suitable base material having an uneven mold surface is used. The substrate can be a single layer of plastic, paper, metal, etc., or any composite made of these, or a layer of polyolefin resin such as polyethylene, polypropylene, or silicone resin on one side of the above single layer or composite, if necessary. A laminated version of these is used as a release layer. In order to form irregularities on one side of these substrates, a known method such as lamination of convexes (turns) by embossing or printing may be used.

Any shape can be used for the unevenness, but
A typical shape is one that imitates the surface condition of natural leather, or it may be one that imitates the surface state of natural leather, or one that has undergone processing such as sewing.

To explain the electron beam curable composition used in the present invention, one composition mainly uses a prepolymer or oligomer having ethylenically unsaturated bonds in the molecule, and ethylenically unsaturated bonds are added to adjust the viscosity. A monomer having the following properties is used as appropriate. The composition used in the present invention soaks into the permeable substrate (described below) moderately after application, does not impair the texture of the permeable substrate, and has good reproducibility of unevenness in the final product obtained. desired. From this point of view, the viscosity of the composition at room temperature (2s °C) is 10θ.
It is desirable to use one having a value of 00c, p, s1 or more. If the viscosity is less than 1000 θCm Pg S-, the composition will penetrate excessively into the permeable base material, impairing the feel of the permeable base material, and also reducing the reproducibility of the important irregularities. The upper limit of the viscosity of the 1s composition should be determined from the suitability for hot melt coating.
0:000 c, p, s.

In order to obtain a composition having a viscosity within the above range, a prepolymer or oligomer having an ethylenically unsaturated bond in the molecule is required. It is preferable to set it to less than SO Jusho%.

A prepolymer having an ethylenically unsaturated bond is an oligomer, and specific examples include the following compounds: unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates , various acrylates such as melamine acrylate, various methacrylates such as polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, melamine methane 1 route.

The seven polymers having an ethylenically unsaturated bond in the molecule have the ability to dilute the above prepolymer or &i,4-IJ sesame, and impart mechanical strength such as cohesive force to the coating after curing. The following compounds may be cited as specific examples; butylcarbamoylethyl acrylate, ethylcarbamoylethyl acrylate, phenylcarbamoylethyl acrylate-1-nato-sigma urethane acrylates, phthylcarbamoylethyl acrylate, Methacrylate, ethylcarnomoylethyl methacrylate, phenylcalci (urethane methacrylates such as moylethyl methacrylate, hydroxyethyl acrylic V-), hydroxyacrylates such as hydroxypropyl acrylate, ethylene glycol resin acrylate-1, propylene glycol di acrylate, neohentyl glycol diacrylate), /, 4
- polyfunctional compounds such as hexanediol diacrylate, triethylene glycol diacrylate, neobentyl glycol dimethacrylate, triethylene glycol dimethacrylate, and/or thiol compounds such as trinotyl p-propane trithioglycolate, penquerythritol Tetrathioglycolate.

The above-mentioned prepolymers or oligomers and monomers can be used alone or in combination to form a composition.

A polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or benzoquinone may be added to the composition as a stabilizer in order to prevent curing from proceeding before electron beam irradiation. or,
A coloring agent such as a pigment or dye may be added to the composition in a range of S to 30 M, % lization, for coloring the composition. If the weight is less than 5 weight, the coloring effect will be weak and the hiding power will be poor. If the weight exceeds 300 weight, the curability of the composition will decrease.

Uneven pattern? The above viscosity is 10θθ on the preformed mold material.
To apply a composition with θc, p, s0 or more, a hot melt method is used, in which the composition is heated to a high temperature to reduce its viscosity to a level that allows it to be coated.The coating head method includes roll coating and gravure coating. These methods include court, fountain court, etc. As the heating temperature of hot melt b! s
The coating amount is generally 1.20 to isoμ7+1, depending on the degree of unevenness of the mold material.

After applying an electron beam curable composition to the uneven surface of the mold material, a permeable base material is laminated on the applied surface.

Fibrous materials such as non-woven fabrics, woven fabrics, or composite materials of non-woven fabrics and woven fabrics are used as the permeable material, but in addition, non-woven fabrics or woven fabrics with a synthetic resin foam layer can also be used. If you use something like this, you will get a product that is soft to the touch.

Examples of nonwoven fabrics include those made of fibers such as polyester, rayon, nylon, or aromatic polyamide;
Or paper. Examples of woven fabrics include fabrics made of fibers such as acrylic, polyester, cotton, nylon, or rayon, or blends of these fibers 4A'.

The laminating method may be carried out, for example, by unrolling a roll of permeable base material (S), guiding it onto the coating surface, and pressing it with a rubber roll or metal roll as required.

Next, the laminate is irradiated with an electron beam to heat the composition in the laminate to form a cured product. As a source for electron beam irradiation, a low-energy electron accelerator,
For example, Electrocurtain CBλo/so'/3θ manufactured by Energy Science Co., Ltd. or NP-ESH/30 manufactured by Ottodur can be used, and electron beam irradiation is preferably performed in a nitrogen gas atmosphere. , Also, irradiation lvi! The amount is 05~. 7'
OMrad is fine.

Incidentally, the electron beam irradiation may be performed from either side of the laminate (that is, it may be performed from the mold side or the permeable substrate side. Also, it may be performed from both sides.

After electron beam irradiation, the cured product integrated with the permeable base material is peeled off from the mold material to obtain a synthetic resin composite sheet having irregularities on the surface and permeable profit margin on the back surface.

(Effects of the Invention) According to the method of the present invention described below, since an electron beam curable composition having a viscosity of /0000 c, p, s, or less, Even after lamination with permeable profiteering, there is little penetration of the composition into the base material, and the sense of profiteering is not impaired. A part of the material will not be exposed to the mold surface VC and the unevenness of the product will not be impaired.

(Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 The following composition was applied to the side of a mold obtained by embossing a polypropylene laminated paper with a shape of natural leather, and the following composition was heated to a temperature of SO ℃, and the coating amount was 30 to 30℃. It was Kubobu. The viscosity at 30°C is i
a,oo.

c, p, s.

Next, a polyester satin woven fabric was laminated on the applied surface at room temperature, and after lamination, Electro Curtain CB Yuoo/so/3o manufactured by Energy Science Co., Ltd. was applied from the woven fabric side.
The sample was irradiated with a 1L beam of /OMrad in a nitrogen atmosphere using a

After the irradiation, the mold material was removed to obtain a synthetic leather having a leather-like unevenness on the surface and having a woven fabric as a base material.

A similar synthetic leather was obtained by carrying out the same procedure as in Example 1 except that polyethylene laminate paper embossed was used as the Ichimugi JL No-shaped material and the following composition was used. The viscosity of the composition at 5θ°C was /l Of.

Composition Comparative Example The following composition was used for hair, and the other procedures were the same as in Example 1. The viscosity of the composition at 30°C is
θc, p, t.

Composition However, the above-mentioned composition has significant impregnation with the woven fabric, and the back side of the resulting product is resinized, and
The +lr appearance of the unevenness of type 4'A was extremely poor.

[Brief explanation of drawings]

FIG. 1 is a conceptual diagram for explaining the present invention in detail. l・・・・・・・・・Mold material 2・・・・・・Concave Convex surface 3・・・・・・・・・Hot melt applicator ke・
・・・・・・・・・Electron beam curable m parabolic S・・・・・・
...... Permeable base material 6 ...... Electron beam irradiation device ...
・・・・・・Hardened product patent applicant Dai Nippon Printing Co., Ltd.

Claims (1)

[Claims] (1) The viscosity at room temperature /
An electron beam curable composition of 0.000 c, p, s or more is applied, then a permeable base material is laminated on the coated surface, the entire surface is irradiated with an electron beam, and then the mold material is bonded to the base material. A method for producing a synthetic resin composite sheet, characterized by peeling off an integrated cured product.