JPH06166156A - Vinyl chloride resin compound - Google Patents

Abstract

PURPOSE:To ensure that a vinyl chloride resin compound which has no deterioration in coagulative power and exhibits superb adhesive properties even after the lapse of days by adding an adhesive layer prepared by emulsifying and polymerizing a vinyl chloride resin molded body containing plasticizer and a blend of acrylic ester and other monomer. CONSTITUTION:A vinyl chloride resin molded body containing plasticizer and a monomer blend of (a) 60 to 99.5wt.% one or more than two types of alkylester acrylate monomer with the 9 or less number of carbons of an akyl group, 0.1 to 10wt.% of (b) one or more than two types of selected monomer of polyfunctional monomers, and one or more than two types of ethylene unsaturated monomer other than (a) and (b), are polymerized by emulsification using a reactive surfactant. In addition, a pressure-sensitive adhesive layer based on an emulsion of acrylic copolymer with -30 deg.C max. of glass transition temperature is added to produce a vinyl chloride resin compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention requires a vinyl chloride resin molded product containing a plasticizer and a pressure sensitive adhesive composition suitable for adhering the molded product to another adherend. The present invention relates to a resin composite, and the composite is considered to be useful for industrial, agricultural, medical and other purposes by utilizing its function.

[0002]

2. Description of the Related Art Conventionally, when a vinyl chloride resin molded article containing a plasticizer is adhered to another adherend, a pressure sensitive adhesive composition mainly composed of rubber or synthetic resin has been used. Is insufficient in the initial adhesive properties, or the plasticizer in the molded article migrates into the adhesive composition over time, and as a result, the adhesive properties after aging, particularly the cohesive strength, are significantly reduced. There were drawbacks such as contamination and creep of the body.

[0003]

In view of the above situation, the present invention provides not only initial adhesive properties to vinyl chloride resin moldings containing a plasticizer, but also cohesive strength after aging. The present invention has been made in order to provide a vinyl chloride resin composite in which a pressure-sensitive adhesive capable of exhibiting excellent adhesiveness without deterioration is combined.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a monomer is used in a specific range and a reactive surfactant is used as a surfactant to initiate radical polymerization. A composition mainly composed of a specific range of acrylic copolymer emulsion emulsion-polymerized in the presence of an agent,
It was found that the problem could be solved by combining with a vinyl chloride resin molded product containing a plasticizer, and further the monomer and the type and amount of the reactive surfactant were tested to arrive at the present invention. .

That is, the present invention has solved the above-mentioned problems. This is because (A) a plasticizer-containing vinyl chloride resin molding and (B) (a) an alkyl group having 9 or less carbon atoms (meta). ) One or more monomers selected from alkyl acrylate monomers 60 to 99.5% by weight (b) One or more monomers selected from polyfunctional monomers 0.1 to 10% by weight (C) One or more ethylenically unsaturated monomers other than the above (A) and (B)
Emulsion polymerization of a monomer mixture consisting of the balance [(a) to (c) in total of 100% by weight] in the presence of a radical polymerization initiator using a reactive surfactant as a surfactant, Vinyl chloride resin composite formed by combining with a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer emulsion having a glass transition temperature of −30 ° C. or less as a main component. , Is the gist.

The present invention will be described in detail below. There is no particular limitation on the plasticizer-containing vinyl chloride resin molded body that is the constituent element (A) in the composite of the present invention.
By adding a known plasticizer and various additive components to a conventionally known vinyl chloride-based resin, it is possible to use any one of molded products obtained by a known preparation / molding method. That is, a predetermined proportion of a blending component is uniformly dispersed by a blending machine such as a ribbon blender, a Henschel mixer, a high-speed mixer, or a kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a pressure kneader. A composition for molding is prepared by a method such as homogeneously kneading and dispersing, and then molded into a desired form using an extrusion molding machine, an injection molding machine, a calender molding machine, or a vinyl chloride paste resin and a plasticizer. It is possible to use a molded product using a vinyl chloride paste composed of various additives.

Examples of the vinyl chloride-based resin for the plasticizer-containing vinyl chloride-based resin molding include vinyl chloride homopolymer,
Examples thereof include a post-chlorinated vinyl chloride polymer and a copolymer with a monomer copolymerizable with vinyl chloride. Further, as long as the vinyl chloride resin is contained in an amount of 50% by weight or more, it may be a blend or alloy with another resin such as an acrylic resin or an olefin resin such as chlorinated polyethylene. These vinyl chloride resins may be used alone or in combination of two or more.

Examples of the copolymerizable monomer in the above copolymer include, for example, vinyl acetate, vinyl propionate and other fatty acid vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate and other alkyl (meth) acrylates. Α such as ester, ethylene and propylene
-Olefins, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and the like.

The plasticizer is also not particularly limited and may be arbitrarily selected from those conventionally used for vinyl chloride resins. Examples of such a plasticizer include phthalic acid ester-based compounds such as dibutyl phthalate, dioctyl phthalate, dinonyl phthalate and diisodecyl phthalate, aliphatic dibasic acid ester systems such as dioctyl adipate and dioctyl sebacate, tricresyl phosphate, and tricresyl phosphate. Examples thereof include phosphoric acid ester type such as octyl phosphate, epoxy type such as epoxidized soybean oil, trimellitic acid type and polyester type. These plasticizers may be used alone,
You may use it in combination of 2 or more type.

Furthermore, if desired, it is optional to add various additive components conventionally used for vinyl chloride resins, such as stabilizers, fillers, lubricants, colorants and modifiers.

The (meth) acrylic copolymer in the emulsion, which is the main component of the composition for forming the pressure-sensitive adhesive layer which is the constituent element (B) in the composite of the present invention, is
As described above, it is composed of the components (a) to (c), but as the (meth) acrylic acid alkyl ester monomer having an alkyl group having a carbon number of 9 or less, which is the component (i), methyl (meth) acrylate, Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth)
Isobutyl acrylate, hexyl (meth) acrylate,
Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate,
Illustrative is isononyl (meth) acrylate, and of these, only one kind or a combination of two or more kinds can be used. In order to achieve the object of the present invention, the amount or the total amount of the (meth) acrylic acid alkyl ester monomer is 60 to 99.5% by weight of the total amount of the monomer, but preferably 65 to 90% by weight. Is.

The component (b), which is a polyfunctional monomer, includes a carboxyl group or its anhydride, a hydroxyl group, an amide group, an amino group, an alkoxyl group and a glycidyl group in addition to a radically polymerizable unsaturated group in one molecule. Having functional groups such as
And having two or more radically polymerizable unsaturated groups in one molecule.

Examples of such polyfunctional monomers include monomers containing a carboxyl group such as acrylic acid, methacrylic acid and maleic anhydride or anhydrides thereof, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. A hydroxyl group-containing monomer such as (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide,
Amide group-containing monomers such as N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide,
Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, alkoxyl group-containing monomers such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, glycidyl (meth) acrylate In one molecule such as glycidyl group-containing monomer such as glycidyl allyl ether, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Examples thereof include monomers having two or more radically polymerizable unsaturated groups. Among these, the polyfunctional monomers may be used alone or in combination of two or more.

The amount of the polyfunctional monomer used is based on the total amount of the monomers.
The amount is 0.1 to 10% by weight, preferably 0.1 to 5% by weight. If it is less than 0.1% by weight, sufficient holding force cannot be obtained, and if it exceeds 10% by weight, sufficient adhesive force cannot be obtained with respect to the vinyl chloride resin molded product.

The component (c) is an ethylenically unsaturated monomer other than the components (a) and (b), and imparts physical properties and coating film characteristics that cannot be exhibited by the components (a) and (b) alone. However, in order not to impair the object of the present invention, 35% by weight or less of the total amount of the monomers is usually used. More preferably, it is 30% by weight or less. Examples of such a monomer include acrylonitrile, styrene, styrene derivatives, vinyl acetate, vinyl propionate and the like.

In addition to these, tackifying resins such as rosin-based, petroleum resin-based, coumarone-indene resin-based, and phenol resin-based resins may be added to the monomer and used, if necessary.

Examples of reactive surfactants for producing the emulsion which is the main component of the pressure sensitive adhesive used in the present invention include:

[Chemical 1]

[0018]

[Chemical 2] Anionic reactive surfactants such as, and

[0019]

[Chemical 3] And non-ionic reactive surfactants.

This reactive surfactant may be used alone or in combination of two or more kinds, but if the amount is too small, a lot of coagulates will be generated in the produced emulsion, and thus it will be obtained. The resulting coating also does not exhibit good physical properties. Also, when the amount is too large, the particle size of the polymer becomes fine, the viscosity of the emulsion rises too much, the polymerization rate decreases, and the water resistance of the film also deteriorates. Therefore, the amount of this reactive surfactant used should be 0.5-0.5% of the total monomer.
15% by weight is preferable, and 1 to 7% by weight is particularly preferable.

The reactive surfactant is used in an amount of 20% by weight based on the amount used, as long as the object of the present invention is not impaired.
It is possible to use a combination of surfactants which are usually used in emulsion polymerization only when the amount is less than the above. Examples of such a surfactant include anionic surfactants such as alkyl or alkylallyl sulfates, alkyl or alkylallyl sulfonates, and dialkyl sulfosuccinates, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl ethers. Examples thereof include nonionic surfactants such as oxyethylene carboxylic acid ester.

As the radical polymerization initiator for producing the emulsion used in the present invention, persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide solution, t-butyl hydroperoxide, hydrochloric acid of azobisamidinopropane Water-soluble types such as salts, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide,
Examples include oil-soluble types such as diisopropyl peroxydicarbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, and azobisisobutyronitrile. Furthermore, if necessary, a redox system in which a reducing agent such as N, N-dimethylaniline, sodium acid sulfite, Rongalit, and ascorbic acid is also used can be used. The amount of the polymerization initiator used is usually 0.01 to 5% by weight with respect to all the monomers, but more preferably
It is 0.05 to 2% by weight.

To prepare an emulsion of a (meth) acrylic copolymer, which is the main component of the pressure-sensitive adhesive used in the present invention, first, the above-mentioned various monomers are mixed, and the reactive surface-active agent is added thereto. Add an agent, a polymerization initiator, etc. and polymerize in an aqueous system.
In this case, various methods such as a batch polymerization method and a method of continuously supplying each component can be applied. The polymerization is usually carried out at a temperature of 10 to 90 ° C with stirring.

The glass transition temperature of the (meth) acrylic copolymer obtained by polymerization must be -30 ° C or lower, and if the temperature is higher than -30 ° C, good adhesive strength cannot be obtained. . The glass transition temperature is determined by the following formula. 1 / Tg = Σ (Wi / Tgi) Tg: glass transition temperature of copolymer (absolute temperature display) Tgi: glass transition temperature of homopolymer of monomer component (i) (absolute temperature display) Wi: co-weight Weight fraction of component (i) in coalescence (B. Am. Phys. Soc. Vol.
According to the method of G. Fox. )

If necessary, a compound containing a divalent or higher metal ion such as Ba, Ca, Zn, Mg, Al, Zr, Cu or Fe, or an aziridine compound may be added to the emulsion after the polymerization to crosslink it. Good. In this emulsion, if necessary, a thickener, a defoaming agent, a pigment such as titanium oxide, a plasticizer, a rosin type, a petroleum resin type, a coumarone indene resin type,
A tackifying resin such as a phenol resin type can be added and blended. The pressure-sensitive adhesive composition is obtained as described above.

The pressure-sensitive adhesive composition prepared as described above is impregnated onto the surface of the plasticizer-containing vinyl chloride resin molding, spraying, reverse roll coater, bar coater, knife coater, screen printing, and the like. An example of the vinyl chloride-based resin composite of the present invention can be obtained by forming the pressure-sensitive adhesive layer by applying a coating by a usual treatment method and drying it. The coating amount of this pressure-sensitive adhesive composition is preferably 5 to 100 g / m ² , more preferably 10 to 70 g as the coating amount after drying.
The range is / m ² . In the vinyl chloride resin composite of the above example, the pressure-sensitive adhesive layer is protected by a film or the like, or a plasticizer-containing vinyl chloride-based resin molded product and other coatings via the pressure-sensitive adhesive layer described above. A plasticizer-containing vinyl chloride resin molded product, such as a composite in which a body (including a plasticizer-containing vinyl chloride resin molded product) is bonded (including temporary adhesion), and the above-mentioned pressure-sensitive adhesive layer Complexes are within the scope of the invention.

[0027]

EXAMPLES The present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the examples. In the examples, parts and% are parts by weight and% by weight, respectively.
Indicates.

Example 1 A polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet was charged with 91.5 parts of deionized water and the reactive surfactant Eleminol JS-2 [manufactured by Sanyo Chemical Industry Co., Ltd., trade name. ] 2.6 parts, reactive surfactant ADEKA REASOAP NE-
2 parts of 10 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) were charged, the temperature was raised to 70 ° C. with stirring to dissolve the mixture, and then nitrogen substitution was performed.
To this, 3 parts of a 1% aqueous solution of ferrous sulfate and 10 parts of a 1% aqueous solution of ascorbic acid were added, and at the same time, 87 parts of 2-ethylhexyl acrylate, 10 parts of vinyl acetate, 2 parts of acrylic acid, 1 part of glycidyl methacrylate were added. And 0.1 part of benzoyl peroxide were uniformly added dropwise over 3 hours, and the reaction was continued at 70 ° C. for 2 hours to complete the polymerization.
The solid content concentration of the obtained emulsion was 49.8%.
The glass transition temperature of the copolymer was -59.0 ° C.

The reactive surfactant used for the polymerization has the following structure.

[Chemical 4]

The emulsion obtained above was applied on the surface of a soft polyvinyl chloride film containing 50 PHR of a plasticizer dioctyl phthalate having a thickness of 50 μm by a bar coater so that the dry film thickness was 25 g / m ^2, and then at 100 ° C. A test piece was dried for 2 minutes. With respect to the obtained test piece, the adhesive force and the holding force were measured at the initial stage and after the passage of time. The results are shown in Table 2. In addition, the measurement of each characteristic was performed as follows.

A. Adhesive strength A test piece cut into a strip with a width of 25 mm and JIS Z 152
The SUS plates adjusted in accordance with 8 are stacked, and a 2 kg rubber roller is reciprocated once at a speed of 300 mm / min for pressure bonding and bonding. After leaving for 20 minutes, 300 according to JIS Z 1528
Measure the force to peel the adhesive surface 180 degrees at a speed of mm / min.
Further, the bonded sample is left in an atmosphere of 50 ° C. and 85% RH, and the adhesive strength after 2 days, 7 days, and 14 days is measured by the same method.

B. Holding power test piece and SUS adjusted according to JIS Z 1528
Laminate the plates so that the combined area is 25 mm × 25 mm,
A 2 kg rubber roller is reciprocated once at a speed of 300 mm / min to bond it. After leaving for 20 minutes, JIS Z 1528
According to the above, a load of 1 kg is applied to one end of the test piece in an atmosphere of 40 ° C., and the time until the adhesive surface is sheared off is measured. Furthermore, the bonded samples are left in an atmosphere of 50 ° C. and 85% RH, and the holding power after 2, 7, and 14 days is measured by the same method.

Examples 2 to 4 and Comparative Examples 1 to 3 In the same manner as in Example 1, the monomers, additives and
An emulsion was prepared by polymerizing with the kind and amount of the surfactant. The properties of the obtained emulsion were evaluated in the same manner, and the results are shown in Table 2.

[0034]

[Table 1]

The reactive surfactant in Table 1 has the following structure.

[Chemical 5]

[0036]

[Table 2]

Example 5, Comparative Example 4 100 parts of vinyl chloride resin, 35 parts of dioctyl phthalate, 5 parts of epoxy plasticizer, and 3 parts of Ba-Zn stabilizer were blended in a blender and kneaded in a Banbury mixer to obtain T. A 0.15 mm thick soft vinyl chloride film was made with a die extruder. Next, the (meth) acrylic emulsions obtained in Example 1 and Comparative Example 1 were separately coated on one side with a reverse roll coater so that the dry coating film thickness would be 40 g / m ² and dried to obtain pressure-sensitive adhesion. A vinyl chloride film coated with the agent was obtained. Both films are made of SUS B for kitchen sink
It was used as a protective film for A plate, and after being stored for 3 months, the state when peeled off was observed, and the above pressure-sensitive adhesive coated film was slit into 50 mm width and used as an adhesive tape to seal the box, then at 60 ° C. Table 7 shows the results obtained by observing the condition when the product was stored in the dryer for 7 days and taken out.

[0038]

[Table 3]

Example 6, Comparative Example 5 65 parts of vinyl chloride paste resin, 35 parts of vinyl chloride resin, 60 parts of dioctyl phthalate, 1 part of Ba—Zn stabilizer, foaming agent
After impregnating the back surface of a polypropylene carpet with a PVC paste composed of 0.7 parts and 50 parts of calcium carbonate, it was heated and foamed to produce a tile carpet. Then, the (meth) acrylic emulsions obtained in Example 1 and Comparative Example 1 were separately applied to the foamed vinyl chloride surface by a reverse roll coater so that the thickness of the dried coating film would be 60 g / m ² and dried to obtain pressure sensitivity. An adhesive coated tile carpet was obtained. These tile carpets were applied to floors made of various materials, and the state of peeling and reattaching after 6 months was observed. The results are shown in Table 4.

[0040]

[Table 4]

[0041]

INDUSTRIAL APPLICABILITY According to the present invention, a pressure-sensitive adhesive capable of exhibiting excellent adhesiveness not only in the initial adhesive properties but also in the adhesive properties of a vinyl chloride resin molded product containing a plasticizer is obtained. A novel vinyl chloride resin composite is provided. Due to this characteristic, the vinyl chloride resin composite of the present invention is extremely advantageous in practical use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 2/24 MCB 7442-4J 220/18 MLY 7242-4J // C09J 133/08 JDE 7921-4J (72) Inventor Nobuyuki Takahata 2-17-33 Kitafu, Takefu City, Fukui Prefecture Nisshin Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A type selected from (A) a plasticizer-containing vinyl chloride resin molding and (B) (a) a (meth) acrylic acid alkyl ester monomer having an alkyl group having 9 or less carbon atoms, or Two or more monomers 60 to 99.5% by weight (B) One or more monomers selected from polyfunctional monomers 0.1 to 10% by weight (C) Above (A) and (B) 1) or 2 or more kinds of ethylenically unsaturated monomers other than
Emulsion polymerization of a monomer mixture consisting of the balance [(a) to (c) in total of 100% by weight] in the presence of a radical polymerization initiator using a reactive surfactant as a surfactant, Vinyl chloride resin composite formed by combining with a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer emulsion having a glass transition temperature of −30 ° C. or less as a main component. .