JPH0563309B2 - - Google Patents

Description

[Detailed description of the invention]

[0001]

TECHNICAL FIELD The present invention relates to a polyvinyl chloride film (hereinafter referred to as "PVC film") laminate with improved post-processability and a method for producing the same.

[0002]

2. Description of the Related Art Adhesives are used in the production of PVC film laminates, such as PVC steel plates. Conventionally, this adhesive is generally a thermosetting type that contains organic solvents such as ethyl acetate, methyl ethyl ketone, toluene, and xylene. It had drawbacks such as the embossed pattern on it disappearing and the lamination of thin PVC film being difficult.

[0003] In recent years, electron beam curable adhesive compositions that are solvent-free and do not require heating (room-temperature curable) have been proposed.

[0004] For example, in JP-A-57-172969 and JP-A-58-174475, electron beam curable adhesive compositions containing polyacrylates such as urethane polyacrylate and polyol polyacrylate as main components are disclosed. Further, JP-A-56-127674 discloses an electron beam curable adhesive composition comprising a radically polymerizable prepolymer, a vinyl acetate polymer, and a plasticizer.

[0005] Therefore, it is conceivable to obtain a PVC film laminate using these electron beam curable adhesive compositions.

[0006]

[Problems to be Solved by the Invention] However, the above-mentioned conventional electron beam curable adhesive compositions do not have sufficient flexibility of the cured product or do not have sufficient adhesion to the PVC film, so the resulting laminated layer There is a risk that the PVC film may peel off when the body is subjected to post-processing such as bending or drawing. Furthermore, in the case of adhesives using plasticizers, the plasticizer bleeds out over time, which may cause deterioration of the bonded PVC film and reduce the quality of the laminate.

[0007] The present invention eliminates the above-mentioned drawbacks, and aims to provide a PVC film laminate that can perform good post-processing without peeling of the PVC film and can maintain good quality for a long period of time. .

[0008]

[Means and effects for solving the problem] For this purpose, in the invention of claim 1, (A) at least one of an acrylic acid ester monomer and a methacrylic acid ester monomer, (B) a vinyl chloride-based monomer soluble in the above monomer. A copolymer, (C) a linear polyurethane resin soluble in the above monomer, and an electron beam curable adhesive composition containing the above (A), (B) and (C) as essential components, are applied to a PVC film and a board material. After bonding the PVC film and the plate material, the adhesive composition is irradiated with an electron beam from the PVC film side to cure the adhesive composition and join the PVC film and the plate material. This is what we plan to do.

[0009] Furthermore, in the invention of claim 2, there is provided a PVC film laminate in which a PVC film and a plate material are bonded together by a cured product of the electron beam curable adhesive composition.

[0010] In the following explanation, (meth)acrylate is a general term for acrylic acid ester monomers or methacrylic acid ester monomers, and the content displayed with a bracket in the substance name is treated in the same way as this (meth). .

[0011] Examples of the (meth)acrylate used in the adhesive composition of the present invention include alkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and glycidyl (meth)acrylate.
Acrylate, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate,
Tetrahydrofurfuryl (meth)acrylate,
2-hydroxy-3-phenyloxypropyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, ( poly)
ethylene glycol di(meth)acrylate,
(Poly)propylene glycol di(meth)acrylate, 1,6-hexanediol(meth)acrylate, trimethylolpropane tri(meth)acrylate
Examples include acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl glycol di(meth)acrylate, various urethane(meth)acrylates, epoxy(meth)acrylate, polyester(meth)acrylate, etc. However, it is not limited to these, and one or more of these may be used in combination.

[0012] If necessary, vinyl monomers other than the above (meth)acrylates, such as (meth)acrylic acid, maleic acid, (meth)acrylamide and its derivatives, styrene, divinylbenzene, N
-Vinylpyrrolidone etc. may be used, but the amount of these monomers is preferably 50 parts by weight or less, and 50 parts by weight or less per 100 parts by weight of the monomers used in the adhesive composition.
If it is used in excess of parts by weight, the purpose of the present invention may be impaired.

[0013] The vinyl chloride copolymer used in the adhesive composition of the present invention is not particularly limited as long as it is a vinyl chloride-based polymer that can be dissolved in the monomer used in the adhesive composition.
Preferred examples include vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers and other modified monomers, and saponified products thereof.

[0014] As the above modified monomer, (anhydrous)
Acidic monomers such as maleic acid, (anhydrous) itaconic acid, (meth)acrylic acid, and (meth)acryloyloxyethyl acid phosphate are common, and if one of the adherends is a metal, these modified It is preferable to use a polymer obtained by copolymerizing a small amount of monomers.

[0015] The linear polyurethane resin used in the adhesive composition in the present invention is generally obtained by an addition reaction between diisocyanate and diol, and the (meth)acrylate resin used in the adhesive composition There is no particular restriction as long as it is soluble in.

[0016] Examples of the diisocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,5
- Naphthalene diisocyanate, xylene diisocyanate, and prepolymers of these diisocyanates. Examples of the diols include (poly)ethylene glycol, (poly)propylene glycol, copolymers of ethylene oxide and propylene oxide, glycols such as 1,4-butanediol and 1,6-hexanediol, and adipic acid. , polyester type polyols obtained by the esterification reaction of dicarboxylic acids such as phthalic acid and isophthalic acid with glycols, liquid polybutadiene resins with hydroxylated terminals, and castor oil.

[0017] The amount of vinyl chloride copolymer and linear polyurethane resin used in the adhesive composition is 1 to 60 parts by weight and 0.5 to 40 parts by weight, respectively, per 100 parts by weight of the monomer used in the adhesive composition. If the amount of the vinyl chloride copolymer and linear polyurethane resin used is less than the above range, the flexibility of the cured product and the adhesiveness to the PVC film will decrease, and the post-processability of the PVC film laminate will deteriorate. On the contrary, if it exceeds the above-mentioned range, the viscosity of the composition becomes too high and the coating workability becomes poor.

[0018] In the case of the adhesive composition in the present invention,
In addition to the above-mentioned components as long as they do not impair the purpose of the present invention, various additives may be added, such as polymerization inhibitors for improving the storage stability of the composition, organic or inorganic fillers for increasing the volume, and adhesives. A thixotropic agent, a leveling agent, an antifoaming agent, a coloring agent, etc. may be added to improve workability during coating.

[0019] The PVC film laminate of the present invention is obtained by applying the above-mentioned adhesive composition to the adhering surface of either the PVC film or the plate material, or both, and then laminating the PVC film and the plate material. , can be obtained by curing the adhesive composition by irradiating an electron beam from the PVC film side.

[0020] The vinyl chloride film used in the vinyl chloride film laminate of the present invention generally has a thickness of about 10 μm to several hundred μm (including a relatively thick film usually called a vinyl chloride sheet).

[0021] On the other hand, plate materials used for the PVC film laminate of the present invention include cold rolled steel plates, hot rolled steel plates, and various surface-treated steel plates (plated steel plates, painted steel plates, chemically treated steel plates, primer treated steel plates, etc.). )
Generally, steel plates are used, but metal plates other than steel such as aluminum plates, various plastic plates, and wood plates may also be used.

[0022] Furthermore, when manufacturing the PVC film laminate of the present invention, the amount of electron beam irradiation applied to cure the adhesive depends on the thickness of the PVC film, the type of monomer used in the adhesive composition, etc. Although different,
Usually, it is about 1 Mrad to several tens of Mrad. If the amount of electron beam irradiation is too small, the adhesive composition will not be sufficiently cured, whereas if it is too large, the vinyl chloride film may deteriorate.

[0023]

[Examples] The present invention will be explained below with reference to Examples, and all parts in the specification are based on weight.

Example 1 and Comparative Example 1 According to Table 1, adhesive composition a used in Example 1
Adhesive compositions b-1 to b-3 used in -1 to a-4 and Comparative Example 1 were prepared. Next, these adhesive compositions were applied onto a steel plate treated with a polyester resin primer, and a PVC film with a thickness of 0.1 mm was laminated thereon. After that, a 7 Mrad electron beam was irradiated from the PVC film side (acceleration voltage: 200 KeV). ) The adhesive composition was cured to produce a PVC film laminate.

[0025] Using this PVC film laminate,
A peel test and an Erichsen test as specified in JIS K 6744 were conducted, and the results shown in Table 2 were obtained.

[0026] ■■■ Turtle shell [0017] ■■■

[0027] ■■■ Turtle shell [0018] ■■■

Example 2 10 parts of partially saponified vinyl chloride-vinyl acetate-maleic acid copolymer (copolymerization ratio: 85:14:1, average degree of polymerization: 400) and 10 parts of "Dismocol 400" were prepared in Table 3. An electron beam curable adhesive composition was prepared by dissolving the mixture of acrylate monomers shown below. Next, a PVC film laminate was prepared and tested in the same manner as in Example 1. The test results are shown in Table 4.

【0029】 ■■■ Turtle shell [0019] ■■■

【0030】 ■■■ Turtle shell [0020] ■■■

【0031】

Effects of the Invention As explained above, the PVC film laminate of the present invention can sufficiently withstand post-processing such as bending and drawing, and does not deteriorate over time due to plasticizers, so it is suitable for PVC steel sheets. It is extremely useful in such fields.

Claims (2)

[Claims] Claim 1: (A) at least one of an acrylic acid ester monomer and a methacrylic acid ester monomer, (B) a vinyl chloride copolymer soluble in the above monomer, (C) a linear polyurethane resin soluble in the above monomer, An electron beam curable adhesive composition containing the above (A), (B), and (C) as essential components is applied to the adhering surface of at least one of the polyvinyl chloride film and the plate material, and Polychlorination characterized by bonding the polyvinyl chloride film and the plate material by irradiating the film and the plate material with each other and then irradiating the polyvinyl chloride film with an electron beam to harden the adhesive composition. A method for producing a vinyl film laminate. 2. (A) at least one of an acrylic ester monomer and a methacrylic ester monomer, (B) a vinyl chloride copolymer soluble in the above monomer, (C) a linear polyurethane resin soluble in the above monomer, A polyvinyl chloride film and a plate material are bonded by a cured product of an electron beam curable adhesive composition containing the above (A), (B), and (C) as essential components. Polyvinyl chloride film laminate.