JPS58113278A - Emulsion-type pressure-sensitive adhesive having excellent light resistance - Google Patents

Abstract

PURPOSE:To prepare the titled composition having improved cohesive force, stickiness, adhesivity, and light resistance, by mixing a specific acrylic copolymer emulsion with an ethylene-vinyl carboxylate-acrylic acid ester copolymer emulsion, etc. CONSTITUTION:The objective adhesive is prepared by mixing (A) 40-95pts.wt. of an acrylic copolymer emulsion obtained by the emulsion polymerization of a monomer mixture composed of (a) 50-99.7 (wt%) (meth)acrylic acid ester monomer containing 4-12C alkyl, (b) 0.2-15% copolymerizable monomer composed of alpha,beta-unsaturated carboxylic acid and (c) 0.1-5.0% copolymerizable monomer containing epoxy group, etc. with (B) 60-5pts.wt. of an emulsion of the copolymer of ethylene-carboxylic acid vinyl ester-(meth)acrylic acid ester, etc. and/ or an emulsion of acryl-modified ethylene copolymer obtained by the two-stage polymerization of an acrylic acid ester to an ethylene-vinyl acetate copolymer emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an emulsion-bound pressure-sensitive adhesive having excellent light resistance.

In recent years, there has been an increasing demand for solvent-free adhesives in the field of pressure-sensitive adhesives, and organic solvent-based pressure-sensitive adhesives, which have traditionally occupied an overwhelming proportion, are being replaced by aqueous emulsion-free adhesives.

The performance and properties required for pressure-sensitive adhesives can be broadly classified into two types, one of which is adhesive strength, cohesive strength, and adhesion strength, which are commonly referred to as adhesive performance. It is basic. This is an essential property for functioning as a pressure-sensitive adhesive, and is a property that depends on the viscoelasticity of the pressure-sensitive adhesive.

Another property is a property seen from the functional aspect of the pressure-sensitive adhesive, and is a secondary property.

For example, it is required under the conditions in which labels, stickers, etc. are used, such as the fact that stickers and labels that have been pasted are required not to show color even if they are left on for a long period of time. Properties other than viscoelasticity.

Among tack, which is the primary performance required for pressure-sensitive adhesives, tack is an element that indicates instantaneous wetting to the adherend, cohesive strength is an element that indicates creep resistance, and adhesion is an element that indicates creep resistance. This is an element that shows peeling resistance.

Adhesive force is a physical quantity that depends on the surface tension of the pressure-sensitive adhesive itself and its wetting to the adherend due to its viscous flow. Adhesive force is consumed when peeling off after bonding to the adherend. This is the amount of work of the pressure-sensitive adhesive resin, which is also a physical quantity that depends on viscous flow.

Cohesive force is also a physical quantity that depends on the viscous flow of the pressure sensitive adhesive resin.

However, the adhesive force and adhesion force, which depend on the viscosity term, are generally inversely proportional to the cohesive force. In a pressure sensitive adhesive, these six elements must be balanced.

However, such a well-balanced pressure-sensitive adhesive has not been previously known.

Furthermore, in recent years, the number of plastic products to be adhered to has increased, and among these, 5mmwt olefin products such as polyethylene and 19-propylene account for the majority in terms of safety, raw materials, and low prices. ll19 ester, &! JjJ [Compared to vinyl chloride, etc., adhesive properties are much worse, and it is hoped that a high-performance pressure-sensitive adhesive with excellent adhesive strength even to olefins will emerge, and a solution for pressure-sensitive adhesives is needed. More problems have arisen.

&9 Olefin resins have a low-energy surface, so the pressure-sensitive adhesive that adhesively bonds them is a low-energy surface.
The wetting caused by tension and viscous flow must be sufficiently suppressed, but with acrylic adhesives and pressure-sensitive adhesives, if designed to cause wetting, the cohesive force will decrease; Increasing the cohesive force has the disadvantage that the sag decreases, and this problem cannot be solved simply by devising the combination of monomers.

On the other hand, pressure-sensitive adhesives are mainly applied to release paper treated with silicone or cone resin, and after drying, a base material such as high-quality white paper or plastic film is pressed onto the surface to produce adhesive base paper. It is used in

The adhesive base paper is printed with shapes such as Bleishupel or animals, and incisions are made along the shape.In the case of complicated shapes such as animal shapes, the excess part is removed at high speed as described in step 4. It is used for products such as stickers, adhesive labels, stickers, and stickers.

This incision is made by cutting only the base material and the pressure-sensitive adhesive layer, and the knife is inserted so as not to cut the release paper. Once the layers are glued together again, along with the animal shapes and other parts that must be left when one piece falls off: 1. Peel off, gamma, and paste the price label with a pasting machine. Sometimes, I end up having to peel off the label next to it.

To prevent this, for example, use acrylic materials with strong cohesive force!
If a pressure-sensitive adhesive is used, one pressure-sensitive adhesive layer can be easily cut (referred to as a-cut), so one scrap removal I will be successful, but the adhesive strength and adhesive strength will be insufficient.

Therefore, it is sticky lol! Pressure-sensitive adhesives with strong cohesive strength and easy adhesive removal have become necessary for adherends with poor skin properties.

Among the six properties of pressure-sensitive adhesives, in order to improve adhesive strength, it is known to blend tackifier resins, elastomers, etc.

This has a copolymer resin base that exhibits tackiness, which prevents it from sticking to the adherend, but Lund resin improves the tensile stress of the pressure-sensitive adhesive layer, reducing the amount of work required to break the pressure-sensitive adhesive. The aim is to increase the AM strength by increasing the height.

However, such attempts require a large amount of money in terms of adhesion and tackiness, and if the object to be adhered to is a material with poor tackiness, such as lyolefin resin, However, it is not possible to obtain satisfactory adhesion and adhesion to the adherend while maintaining the cohesive force. appear.

On the other hand, in addition to the demand for extremely high adhesive performance for acrylic adhesives, pressure-sensitive adhesives yellow even after being applied to adhesive labels, stickers, stickers, etc. for long periods of time. It has been requested that there be no damage (hereinafter referred to as light resistance).

The above-mentioned light resistance is a property that is particularly required for applications in which pressure-sensitive adhesives are visible from the back when adhesive labels are applied to transparent adherends, such as labels and stickers applied to transparent plastics, glass, etc. . There are a large number of such applications, such as glass, windshields, automotive glass, etc. If the light resistance of the pressure-sensitive adhesive is poor in these applications, the yellow color of the pressure-sensitive adhesive may make the label invisible, or the product loses its novelty image, drastically reducing its commercial value.

Conventional pressure-sensitive adhesives, including organic solvent-based pressure-sensitive adhesives, have improved adhesive strength, especially to polyolefins.
Adhesive agent, elaszimmer, to improve adhesion
Ethylene-vinyl acetate resin and the like are added, but these resins themselves have good light resistance (but the light resistance of pressure-sensitive adhesives blended with these resins is poor).

In investigating the above-mentioned difficult Wll, the present inventors struggled with the adhesive performance of the pressure-sensitive post-adhesive and found that the cohesive force, that is, the creep resistance, of the pressure-sensitive adhesive resin Primer〇 It depends on the fluidity of the main chain, and the lower the fluidity of the main chain, the greater the creep resistance, and therefore the greater the cohesive force. We believe that this depends on the contact with the adhesive interface, the surface tension of the pressure-sensitive adhesive resin-1°, the Akebonita-Brown motion of the pressure-sensitive post-adhesive glue segment, and the fluidity of the main chain. I believe that by suppressing the flow of the main chain and increasing the effect of Mikuda-Brownian motion, it is possible to improve adhesive strength and adhesion without changing the cohesive force. He conducted a wide range of research on improving sexual performance.

As a result, the present inventors discovered (4) an acrylic copolymer emulsion IC (11
) (a) Ethylene and carboxylic acid vinyl ester are used as essential monomers, and acrylic ester and (or) methacrylic ester, chloride, carbon AILS-
At least one kind of multi-component ethylene copolymer emulsilon copolymerized with one kind selected from higher vinyl carboxylate x or The blended resin emulsion of (A) and φ) is further added to (
0) Acrylic ester and/or methacrylic ester having an alkyl group of carbon WI 4 to 12 and dialkyl! This problem was solved by mixing an acrylic-unsaturated dibasic acid diester copolymer emulsion resin, which is a copolymerization of ureate and/or dialkyl fumarate) and carboxylic acid vinyl ester as essential monomers. The present invention was completed.

That is, the first invention of the present invention is 1 (4) pi) carbon number 4
- Acrylic ester and/or methacrylic ester monomer having 12 alkyl groups 5M9.7 weight -1 ←) Copolymerizable monomer consisting of α, β unsaturated carboxylic acid 0. (c) 0.1-6.0% by weight of a copolymerizable monomer containing an epoxy group, and (c) 0-50fi% of other monomers copolymerized with the above monomer. A Kyodo-kai product obtained by emulsion polymerization of a monomer mixture! 40 to 95 parts by weight of carbon dioxide as a solid content, CI) Gn ethylene-carboxylic acid ester-acrylic ester and (or) methacrylic layer ester co-electrometal emulsion, ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer Combined emulsilon, ethylene-vinyl acetate #-charcoal 111ks-
At least one of +2 higher carboxylic acid vinyl ester co-electropolymer emuldimine, and (or) -) ethylene-vinyl acetate copolymer emulsilone, ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer emulsion, ethylene-vinyl acetate- At least one type of higher carboxylic acid vinyl ester copolymer emulsion having 5 to 12 carbon atoms is combined with one or more types selected from acrylic modified resin emulsions obtained by two-stage polymerization of acrylic esters and/or methacrylic esters. The solid content of the resin emulsion is 6()-5 parts by weight, and if necessary, (0)
Acrylic esters and/or methacrylic esters having an alkyl group having 4 to 2 carbon atoms, and Schiff's kyl maleate and/or dialkyl maleate)
Acrylic-unsaturated dibasic acid diester copolymer emulsion carbonate obtained by copolymerizing carboxylic vinyl ester, optionally a monomer having a functional group and/or a monomer having two or more double bonds. This is an emulsion-type stain-sensitive EE adhesive with excellent light resistance, which is made by mixing 0-sO in the solid content with 0-sO weight part.

The fourth layer is mainly a component that improves wetting and gives adhesiveness to the object to be adhered to, but it is a component that combines the copolymerizable monomer and epoxy group consisting of the GA) ingredient Richibi, β-unsaturated carbon, and the second layer. The copolymerizable monomers contained have the role of increasing cohesive force to improve adhesive cutting, and even if one of them is absent, this property will not be exhibited. cannot be achieved.

Examples of copolymerizable monomers consisting of Tsuru β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, and acidic acid. Examples include leic acid and its 8-7 esters, zumaru and its hafester, and the amount used is o, 1-ti weight arc and (preferably acrylic acid or itaconic acid) based on the total monomer. 1 to 5% by weight.If it is less than 0.2% by weight, crosslinking progresses too much to reduce the degree of crosslinking, resulting in a decrease in tackiness.

As the copolymerizable monomer containing an epoxy group, unsaturated glycidyl esters such as glycidyl esters of acrylic acid, methacrylic acid, itaconic acid or sorbic acid, unsaturated glycidyl ethers such as allyl glycidyl ether, etc. are used. The amount used is 0.1-5.0% by weight based on the total monomers. If it is less than 11% by weight, the degree of crosslinking will be insufficient and sufficient cohesive force will not be obtained, and if it is more than 5.0% by weight, the adhesiveness will decrease.

Examples of acrylic esters and methacrylic esters containing an alkyl group having 4 to 12 carbon atoms include butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexy methacrylate, octyl acrylate, octyl methacrylate, isononyl acrylate, isononyl methacrylate, Examples include vinyl-F laurate. Is the amount used 5N for all monomers? , 7% by weight.

If the weight is 1% by weight, the adhesion will be insufficient, and if it exceeds 7% by weight, the amount of the copolymerizable monomer containing an epoxy group and the α, β unsaturated carboxyl group will be too small.
The cohesive force is insufficient and the glue seems to break.

Although it can be used in combination with other monomers that copolymerize with the above-mentioned monomer, it cannot be used in an amount of 50% by weight or more because there is a risk that the adhesiveness will be insufficient. Copolymerizable monomers that can be used include ethyl acrylate,
Methyl methacrylate, styrene, acrylonitrile,
These include vinyl acetate, vinyl propionate, and vinyl esters of saturated carboxylic acids branched at the a-position.

Further, functional monomers such as N-methylolacrylamide, hydroxy monomer, divinyl monomer, diallyl monomer, etc. can be used in an amount of 0 to 5% by weight.

Pressure-sensitive adhesives are sometimes blended with tackifying agent resins and elastomers in order to provide second-level properties, such as anchoring properties and adhesion to objects to which they are attached, but these are said to have poor light resistance. Pressure-sensitive adhesives also yellow when exposed to light.

Ethylene-vinyl acetate binary co-emulsion is also used for this purpose, but it cannot avoid yellowing due to insufficient light fastness and pourability.

The components used in the present invention are a multi-component ethylene copolymer emulsion and an acrylic modified/bent ethylene copolymer emulsion obtained by two-stage polymerization of an acrylic monolayer, which is used as an anchor for pressure-sensitive adhesives. It not only provides strength and adhesion, but also excellent light resistance.

The blending ratio of @) ingredients for prisoners is in the range of 40 imaginary 116 parts by weight to 95 parts by weight S5 heavy lid part, and 5) ingredients are 60 parts by weight.
If the amount exceeds 5 parts by weight, the adhesiveness or cohesiveness will be impaired.
If the amount is less than 1 part by weight, anchoring properties and adhesion properties will be insufficient.

Sonari: In the furnace explanation, carboxylic vinyl esters include vinyl acetate, propionic vinyl acetate, vinyl acetate, vinyl pivalate, vinyl laurate, and Beoba 10.
(trade name of saturated carboxylic acid vinyl ester with about 10 carbons i1 branched at the α-position/Siel Chemical), etc.

Further, higher carboxylic acid vinyl esters having 82 carbon atoms include vinyl butyrate, vinyl piperate, PEOVA 10, and the like.

In addition, as the acrylic ester or methacrylic ester, ethyl atelylide 1 butyl acrylate F1
Hexyl acrylate-F12-ethylhexyl acrylate, isononyl acrylate, lauryl acrylate,
Examples include methyl methacrylate, butyl methacrylate, hexyl methacrylate F, methacrylate F12-ethylhexyl methacrylate, and isononyl methacrylate.

(B) component ethylene-carboxylic acid vinyl ester-acrylic ester and/or methacrylic ester copolymer (ethylene content 1()-60% by weight, carvone vinyl ester 5G-415 weight arc) , acrylic ester and (11 or)
- 8 to 50 weight methacrylic acid esters are used, preferably ethylene-containing j11
M5 wt%, vinyl acetate 40-60 wt%, acrylic ester and/or methacrylic ester 5-3
The outermost one with 0 weight is good. If the ethylene content is less than 1 heel weight, the adhesiveness will be insufficient, and if it is more than 50% by weight, the cohesive force will be insufficient. If the carboxylic acid vinyl ester is less than 0% by weight of SO, either cohesive force or adhesive strength will be insufficient, and if it is more than 85% by weight, the amount of acrylic ester or methacrylic ester blended will be too small, resulting in a decrease in light resistance. If the amount of acrylic ester and/or methacrylic ester is less than 5% by weight, the light resistance will decrease, and if it is more than 50% by weight, either cohesive force or adhesive strength will decrease.

The ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer has an ethylene content of 1C)-60% by weight, a carboxylic acid vinyl ester MNs weight ratio of 5-
Although 60% by weight is used, preferably one having an ethylene content of 1N55% by weight, vinyl acetate 4NG heavy duty, and vinyl chloride 540% by weight is preferred. If the ethylene content is less than 100% by weight, adhesiveness will be insufficient, and if it is more than 50% by weight, cohesive strength will be insufficient. Carzanic acid vinyl ester is ink ○
If the amount is less than 0% by weight, the adhesion will decrease, and if it is more than 86% by weight, the amount of vinyl chloride blended will be too high and the light resistance will decrease.

If the amount of vinyl chloride is less than 5% by weight, the light resistance will be decreased, and if it is more than 50% by weight, the adhesiveness will be decreased.

As an ethylene-vinyl acetate-higher carboxylic acid vinyl ester copolymer with a number of 5 and 2, the ethylene content is 1 (?
-60 weight, vinyl acetate 5N5 weight, carbon number 5-4
2 higher carboxylic acid vinyl esters are used, preferably ethylene IM 5 weight, vinyl acetate 40-60 weight, Beopa 10 5-80 weight.
% by weight is preferable. If the ethylene content is less than 10% by weight, the adhesiveness will be insufficient, and if the ethylene content is above sO, the cohesiveness will be insufficient. If the weight of Vinegar Vinyl Sumi O is below, the cohesiveness will be insufficient,
When the weight is 8s or more, the amount of higher carboxylic acid vinyl ester having an aIM prime number of 5-12 is too small, and the light resistance decreases.

If the carbon & 5-12 higher carboxylic acid vinyl ester is less than 5% by weight, the light resistance will decrease, and if it is more than 50mJi%, the cohesiveness will be low.

The acrylic modified ethylene copolymer emulsion obtained by two-stage polymerization of acrylic ester and/or methacrylic ester has an ethylene content of 5 to 50 weight arcs,
Vinyl acetate 9! S10S10 quantum molecule-vinyl acetate copolymer emulsion or the above-mentioned ethylene-containing 1L
Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, lauryl acrylate, methyl methacrylate, methyl methacrylate for 1009 parts by weight of the solid content of the ethylene-based terpolymer emulsion of l()-60 weight- , butyl methacrylate, 2-ethylhexyl methacrylate, iso/nyl methacrylate, lauryl methacrylate, etc. 1 to 500 parts by weight, preferably 1 NOO part by weight of acrylic ester and/or methacrylic ester in two steps. good.

By using the two-stage polymerized acrylic ethylene co-electrolyte emulsion as described above, the light resistance of the pressure-sensitive adhesive can be further improved.

Component (0), the 7-acrylic monounsaturated dibasic acid diester copolymer copolymer, is a component that provides anchorage and adhesive properties to the object to which it is attached, similar to component φ), and is a component that provides IAL (B
) JG) has particularly excellent adhesion to polyolefins. Of course, component (0) has no adverse effect on light resistance at all.Component (0), acrylic-unsaturated dibasic acid diester M copolymer emulsion carbon, is an acrylate ester having an alkyl group having 4N12 carbon atoms and/or Methacrylic acid ester, dialkyl maleate and (′*take) dialkyl 7! A copolymer obtained by copolymerizing a monomer having a functional group and/or a monomer having two or more double bonds. As the combined emuldityl and/or methacrylic ester, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, isononyl acrylate, isononyl methacrylate, etc. are preferable, and the lid used is 46- 45% by weight is suitable. If the weight is 65≦ or more, the cohesive force and adhesive force of the pressure-sensitive adhesive obtained by mixing with component (4) will not be sufficient! If it is less than 15% by weight, the tackiness will be impaired.

Examples of the dialkyl maleate and/or dialkyl heptamerate include dibutyl maleate, dioctyl maleate, dibutyl heptamalate, and dioctyl heptamalate.
The appropriate amount is 1H5 weight≦.065% by weight or more will result in insufficient cohesive force, and less than 15% by weight will result in insufficient adhesive force.

As the carboxylic acid vinyl ester, vinyl acetate, vinyl propionate, vinyl pivalin, etc. are used, and vinyl acetate and Beopa 10 are most preferred. The appropriate amount of carboxyl vinyl ester to be used is 115% by weight. If it is used in an amount of 5% by weight or more, the adhesiveness will be impaired, and if it is less than 1% by weight, the adhesive strength will be insufficient.

In component (0), in addition to the above monomers, a monomer having a functional group and/or a monomer having two or more double bonds may be used in a range of 0 to 5% by weight. I can do it. If more than 5% by weight is used, the tackiness will be impaired.

Preferred examples of the monomer having a functional group include acrylic acid, itaconic acid, maleic acid and its halfester, acrylamide and its methylated product, hydroxyethyl atelylate, and vinylpyrrolidone.

Preferred monomers having two or more double bonds include diallylmalenyde (diallyl phthalate), divinylbenzene, ethylene glycol dimethacrylate, methylenebisacrylamide, tetraallyloxyethane, and the like.

The present invention also uses a copolymer emuldityl (2) component obtained by emulsion polymerization in the presence of a chain transfer agent as the acrylic copolymer containing carboxyl groups and epoxy groups of components 1 and (4). The present invention also relates to a second invention.

(When producing the polyacrylate copolymer emulsion of the Xun component by emulsion polymerization, a chain transfer agent is used to increase the number of terminal groups of the polymer, and epoxy groups and carboxyl groups are introduced into the polymer. , by crosslinking between the polymers, and mixing therewith the 6-component ethylene copolymer emulsion of the component (a) and/or the acrylic-based ethylene copolymer emulsion obtained by two-stage polymerization of acrylic, or further as desired. By mixing this with the acrylic-unsaturated dibasic acid diester copolymer emulsion of component (0), the cohesive force is high, especially under high temperature and high concentration conditions, and the adhesive strength and We have discovered that it is possible to replace pressure-sensitive adhesives with even greater adhesive strength and excellent light resistance. - That is, the present invention crosslinks the polyacrylic acid ester copolymer of the Δ component, which exhibits a wetting effect on the object to be adhered, using a crosslinking component to form a huge polymer.
By suppressing the fluidity of the main chain that reduces cohesive force and increasing the cohesive force, we can improve the wetting effect on the adherend by increasing the number of side chains (terminal groups). The effect of Brownian motion restores the adhesion to the adherend, and the effect of mixing component (4) with component (4), component (0), and component (0) provides extremely excellent light resistance. He invented the pressure-sensitive adhesive.

Chain transfer agents having a chain transfer constant of 0.01 or more for styrene used here include dodecyl mercaptan, turyl mercaptan, n-butyl mercaptan, 2-
Ethylhexylthioglycolate, cyclobromomethane, and the like are preferred.

The amount used is preferably 0.01-10 times the total monomer. If the amount is more than 10% by weight, the cohesive force of the pressure sensitive adhesive will decrease, and if it is less than 0.01% by weight, the adhesive force will be insufficient.

The cA)ti, minute, Δ component, 01) component, and (0) component used in the present invention are all copolymer emulsions,
Manufactured by conventional emulsion polymerization method.

(4) and to produce component (4) and component (0),
Normally, a nonionic emulsifier and an anionic emulsifier are used in combination, a water-soluble colloid is added if necessary, and the polymerization is carried out at normal pressure, at high temperature, or by redox.

The monomers used are the above-mentioned acrylic acid ester and (or) methacrylic acid ester monomer containing an alkyl group having 482 carbon atoms, a copolymerizable monomer consisting of α6β unsaturated carlinic acid, and an epoxy group. Copolymerizable monomers containing these, and other monomers copolymerizable with these if necessary, are usually emulsified using a combination of a nonionic emulsifier and an anionic emulsifier to form an emulsified monomer mixture. Advantageous to use.

In order to produce component (4), an appropriate amount of a chain transfer agent may be mixed into the emulsified monomer mixture used above.

(B) Component ethylene copolymer! An autoclave is used to produce Luji Sun, and the emulsifiers include anionic surfactants, nonionic surfactants, water-soluble protection;
Use one or more types of hydride, and reduce the ethylene pressure to about 1O-10.
Emulsion copolymerization is carried out by a conventional method under 0jE pressure.

The ethylene charge in the resin content is INO weight, preferably 2N5 weight, so-called high ethylenic industrial molten resin is suitable for molding.

In particular, as emulsifiers, O, +, S weight - 7-ionic surfactants for monomers other than ethylene, such as dobushitabenzene sulfonate (F), lauryl sulfonate (F), )lium vinyl sulfonate, and 4 to 7 weight percent of a nonionic surfactant, such as a polyoxyethylene nonylphenyl ether emulsifier, a melioxyethylene-l-lyoxypropylene block coelectronic emulsifier, and 0.2 to 1 weight water-soluble protective colloid, such as cellulose derivatives, starch, dextrin derivatives, polyvinyl vinylidene, etc., particularly preferably an average degree of polymerization of 400 to 2800, an average degree of polymerization of 8iS
Preferred are ethylene copolymer emulsions made with ~97% vinyl alcohol.

In addition, in order to perform two-stage polymerization of acrylic acid ester and/or methacrylic acid ester in an ethylene copolymer emulsion, an emulsion in which the acrylic monomer is emulsified in water with an anionic surfactant and a nonionic surfactant is used. What is necessary is just to supply it as a monomer liquid together with a polymerization catalyst, and to carry out high-temperature or redox polymerization.

The pressure sensitive adhesive of the present invention includes pigments, fillers, plasticizers, tackifiers, thickeners, pH adjusters, freeze stabilizers, antifoaming agents,
Preservatives and antifungal agents can be added.

The substrates to be coated with the pressure-sensitive adhesive of the present invention include cloth, high-quality white paper, art coated paper, cast cord paper, woven paper, aluminum laminate paper, l-lyester, piezochloride resin, acetate, polypropylene, Films such as polyethylene are used.

In order to produce a pressure-sensitive adhesive sheet or film using the pressure-sensitive adhesive of the present invention, the viscosity must be approximately 100% o, o
oa centiliter and transfer or directly coat onto the base cloth, paper, or film using a paint coater, doctor coater, or the like.

Adhesive sheets and films made using the pressure-sensitive adhesive of the present invention can adhere to paper, wood, glass, metal, cloth, plastics, fruit surfaces, etc., and have particularly excellent performance against Nigiliolefin. demonstrate.

Next, the present invention will be explained by giving production examples, examples, and comparative examples.

sin example 1 [ethylene-carbon-vinyl ester-
Production of other monomer copolymer emulsions (multi-component ethylene copolymer emulsions)] In an autoclave equipped with a stirrer, 100 parts by weight of total monomers, 64 parts by weight of ion-exchanged water, and sodium dodecylbenzenesulfonate o , y parts by weight, 0.54 parts by weight of polyoxyethylene nonylphenol ether emulsifier,
From 0.18 parts by weight of Go-Sevenol GM-14 (manufactured by Nippon Gosei Kagaku Kogyo ■, partially saponified lipinyl alcohol), 0.06 parts by weight of acetic acid, 0.3 parts by weight of sodium acetate, and 0.58 parts by weight of Ringalite. An aqueous solution was charged, and nitrogen and ethylene substitution was performed under stirring.

Next, heat the system internal temperature to 50°0, and
Among the monomers listed in the column, monomers other than ethylene and 6.2
At the same time, 19.4 parts by weight of a 6% aqueous ammonium persulfate solution was added dropwise uniformly over 4 hours.

During this time, the reaction temperature was adjusted to 50°0 and ethylene was supplied. The ethylene pressure during polymerization was adjusted to 60 to 6 aytgt, ycII+2 depending on the ethylene copolymerization ratio.

The solids concentration of the emulsion found was approximately 54%.

Production example 2 [ethylene/vinyl acetate Kyodo 2? Production of Marji Soton] 1 part O-clay with a stirrer, 7 parts ion-exchanged water
0 parts by weight of polyethylene, 6 parts by weight of diethylene nonyl ether, and 5 parts by weight of vinyl acetate were added, stirred and emulsified, and 0.5 parts by weight of potassium persulfate was added. Add 10 parts of the polymerization initiator solution at 75%, and bring the temperature inside the system to 7000.
Polymerization was started by injecting 1 ethylene under pressure at 60×s/j, and the remaining 45 parts by weight of vinyl acetate and the remaining polymerization initiator solution were uniformly added dropwise over 4 hours.

After the dropwise addition was completed, the mixture was further aged at the same temperature for 1 hour to complete the polymerization. The observed emulsion has a solid content concentration SOS,
The viscosity was 7000F, and the ethylene content in the copolymer was 2 kg.

Production Example Black [Production of Atari Ethylene-based Co-Electric Polymer Maruji Carbon] First surface prepared by the method of Production Example 1 or Production Example 2) (a) Multi-component ethylene-based copolymer emulsion that shows charm Alternatively, 100 parts by weight of the ethylene-acetic acid-hinyl conjugate emulsion in terms of solid content was charged into a container equipped with a stirrer, a reflux condenser, and a dropping funnel, and the mixture was prepared as described in Table 1)(b) Information. Acrylic acid ester corresponding to column 0) and (
Also, G) a predetermined weight part of methacrylic acid ester, an appropriate amount of ion-exchanged water, a polyoxyethylene alkylphenol ether salt 7A) emulsifier 0.5 weight II,
& rioxyethylene nonylphenyl ether emulsifier 0
．． An emulsifying monomer mixture consisting of 5 parts by weight, 0.2 parts by weight of tertiary butyl peroxide, 0.04 parts by weight of a polyoxyethylene nonyl ether emulsifier, and 2.0 parts by weight of ion-exchanged water. A radical initiator dispersion source and 1.8 parts by weight of a 10's sodium bisulfite aqueous solution were uniformly fed over 2 hours.

Stirring was continued for an additional hour to complete polymerization. The solid content concentration of the resulting emulsion was approximately 50%.

Production Example 4 [Production of acrylic-dibasic diester copolymer emulsion] In a container equipped with a stirrer, a temperature needle, a reflux condenser, and a dropping vx-), 100 parts by weight of ion-exchanged water and ruphenyl ether in polyoxyethylene alcohol were added. Add 3 parts by weight of a system emulsifier, an average degree of saponification of 1 m7-89 mol-1, a degree of polymerization of 140, 3 parts by weight of savinyl alcohol, and 0.5 parts by weight of potassium persulfate. Table (1) of the monomer mixture mixed at the monomer composition ratio listed in column (1)
0≦ to start polymerization, and then the system temperature was increased to 1Qo.
The remaining monomer mixture was uniformly added dropwise over 5 hours while maintaining the temperature at The solid content concentration of the emulsion obtained is approximately S.
It was an O attack.

Example 1 a) Into a container equipped with a stirrer, thermometer, reflux condenser, and dropping a-), 67 parts by weight of ion-exchanged water and 10 parts by weight of l-lyoxyethylene phenol ether were charged, and the temperature was raised while stirring. , 4G'E, 9.7 parts by weight of 2-ethylhexyl acrylate, 6 parts by weight of acrylic acid, 0.3 parts by weight of glycidyl methacrylate, 7 parts by weight of polyoxyethylene alkylphenol ether)! A 10% amount of an emulsifying monomer mixture consisting of R agent 2, ol amount g, polyoxyethylene nonylphenyl ether 1.0 part by weight, and ion exchange water 65j 1 part was added.

Then, the temperature inside the system was raised to 65°C, and potassium persulfate was added to 0.
Ten doses of a 4-arc radial polymerization initiator aqueous solution consisting of 4 parts by weight and 9.6 parts by weight of ion-exchanged water were added dropwise to initiate polymerization. After 60 minutes, 90% of the emulsified monomer mixture remains.
% amount and 90% amount of 4% radical polymerization initiator aqueous solution were continuously and uniformly supplied over 4 hours. Stirring was continued for another 1 hour to complete the polymerization, and 10% ammonia water 4.
Cosmetics were adjusted by adding 5 parts by weight. The solids concentration of the emulsion found was 49%, and the viscosity %i was 5000 cP.

(1) Then, by the method of Production Example 1, an ethylene-vinyl acetate-methyl methacrylate copolymer emulsion produced with a monomer composition corresponding to Example 1 in column 11 (Table 1) was mixed with a solid content of 15% by weight. The mixture was mixed and adjusted to a solid content concentration of 49% and a viscosity of 10+000 aP using a thickener.

Example 2 a) In the same polymerization container as in Example 1, 57 ml of ion-exchanged water and 1 m of polyoxyethylene nonylphenyl ether were added.
0 weight II! After charging and stirring, the temperature was raised to 60°C. 96 parts by weight of butyl butyrate, 4 parts by weight of acrylic acid, 0.4 parts by weight of glycidyl methacrylate, polyoxyethylene alkylphenol ether salt 7A) JR additive. 20 parts by weight, 0 parts by weight of polyoxyethylene nonylphenyl ether, 2 ethylhexylthioglyfury (referred to as 2MMTE0), a chain transfer agent similar to styrene (referred to as 2MMTE0), 5 parts by weight of ion exchange ink Approximately 10 parts by weight of emulsifying monomer mixture were added.

Then, the temperature inside the system was raised to 6Sc, and potassium persulfate was added to 0.
A 10-volume aqueous solution of 4% radical polymerization initiator consisting of 4 parts by weight and 9.6 parts by weight of ion-exchanged water was added dropwise to initiate polymerization.

After the weight is reduced, the remaining 90 doses of the emulsified monomer mixture and 4
Continuously add the remaining 9Q% of the radical polymerization initiator aqueous solution to 4%
It was fed evenly over time.

Stirring was continued for an additional hour to complete the polymerization, and 4.5 parts by weight of 10-ammonia water was added to prepare the pyts. The concentration of wl form in the emulsion was 60% by weight,
The viscosity was 2000oP.

1. Then, by the method of Production Example 1, an ethylene-vinyl acetate-vinyl chloride copolymer emulsion produced with a monomer composition corresponding to Example 2 in column (a) of Table 1 was prepared with a solid content weight ratio of 15. % mixing, using thickener, solid content concentration 50
%, viscosity 10. OOOoIImm was adjusted.

Examples 6-5 Emulsions for pressure-sensitive adhesives were prepared according to Examples 1-2 with the compositions shown in Table 1.

Example 6 An acrylic copolymer emulsion produced in accordance with Example 1 with a monomer structure corresponding to Example 6 in column () in Table 1 was added to the first surface (in Table 1) using the method of Production Example 3. The acrylic ethylene-vinegar electrolyte emulsion produced with the monomer composition corresponding to Example 6 in the column was mixed at a solid content of 15% by weight, and a thickener was used to prepare the mixture. Concentration rumored to be 50, viscosity 1 (L
Iwmt to OOOaP.

Example 7 Monomer composition corresponding to Example 7 in column (A) of Table 111,
An acrylic copolymer emulsion produced according to Example 2 and an acrylic modified ethylene-vinyl acetate produced according to the method of Production Example 6 with a monomer composition corresponding to Example 7 in Table 111 (OI) column. - Cyclized vinyl copolymer emulsion and acrylic-unsaturated dibasic acid diester copolymer prepared according to the method of Production Example 4 with a monomer composition corresponding to Example 7 in column (0) of Table 1111 Combination work! mixed with lujisho in a solid content weight ratio of 70:10:20,
Using a thickener, the concentration is 50% and the viscosity is 1 (LOQOo).
〇Example @ ~ 11 Adjusted to 'p'' According to Examples 6 to 7, an emulsion for pressure sensitive adhesive was produced with the layer formation on the IN surface.

Comparative Example 1 An acrylic copolymer emulsion of Example 1, except that the ethylene-vinyl acetate-methyl methacrylate copolymer emulsion carbon of Example 1) was not mixed.

Comparative Example 2 Monomer composition corresponding to Comparative Example 2 in column (4) of Table 1 (1!
Composition with acrylic acid removed from the corresponding composition of Example 1)
Then, to the acrylic copolymer emulsion produced according to Example 1, ethylene-vinyl acetate-produced according to Production Example 1 was added with a monomer composition corresponding to Comparative Example 2 in the first table) column. Methyl methacrylate copolymer emulsion was mixed 15 times in solid content weight ratio, and the solid content concentration was adjusted to 50%, the viscosity was 1G, and 0OOot using a thickener.

Comparative Example 6 Acrylic produced according to Example 1 with the monomer composition corresponding to Comparative Example 6 in the column (in Table 1) (composition in which glycidyl methacrylate-F was removed from the composition corresponding to Example 1) In the copolymer emulsion, an ethylene-vinyl acetate-methyl metatallylene coelectric polymer emulsion layer produced according to Production Example 1 with a monomer composition corresponding to Comparative Example 3 in the first table) column was added. The mixture was mixed with a solid content of 1611G by weight and adjusted to a solid content concentration of 50 and a viscosity of 10*000oP using a thickener.

Comparative Example 4 An acrylic copolymer emulsion produced according to Example 1 with a monomer composition corresponding to Comparative Example 4 in column (4) of Table 1 (same composition as (4) of Example 1) was Monomer composition (used in the present invention) corresponding to Comparative Example 4 in the , 1st table) column
ethylene-vinyl acetate binary copolymer emulsion) prepared according to Production Example 2, 1 liter of the copolymer emulsion was mixed at a solid content weight ratio, and the solid content concentration was adjusted to SG using a thickener. Viscosity 10.000oX4P-adjusted.

Adhesive strength, cohesive force (heat resistance comparison), and cohesive force (moisture resistance comparison) for the pressure-sensitive adhesive emulsion found in Comparative Test Examples 1-11 and the copolymer emulsions obtained in Comparative Examples 1-4.
, adhesion performance tests for adhesion (to stainless steel and polyethylene), and tests for adhesive cutting and light resistance.

The results are shown in Tables 2 and 6.

The test method is as follows.

Preparation of sample: Apply the emulsions obtained in Examples and Comparative Examples to release paper so that the dry coating layer is 25 ± 5 μm.
110? ,, After drying in a hot air circulation dryer for 2 minutes,
A sample was prepared by transferring it to high-quality paper.

Measurement of viscous force: J. According to the DOW method, a sample with a length of 10 am was pasted on a slope with an inclination angle of 30°, and a steel ball with a diameter of 1762 inches was rolled from a device 1° above the slope. The size of the maximum diameter ball that stops at the top! It was displayed in

Measurement of cohesive force: φ280 specified in JxBR6258
The sample was attached to a 1M33o4 stainless steel plate polished with water-resistant abrasive paper so that the lap area was 25 x 25 -, and the sample was pressed with a roller back and forth once.

A static load of IK# was applied to each sample in a 40'C x 8% dish, 70tl: x 8% sushi, and an atmosphere of 11 arcs at 40°C. It was measured.

Measurement of adhesive strength: From J.280 according to R625δ
A stainless steel plate of BUS M04 polished with water-resistant abrasive paper and a polyethylene plate (by the method specified in JIBK676 &
The measurement was performed under the conditions of 5% RH and a peeling rate of 600 wtaAm.

Adhesive cutting test: 1) Cut 1110 sheets on the high-quality paper and adhesive side of the sample with a cutter, sandwich them between two glass plates, and apply 20g1 to the sample at 40°C x 65% RH under zero ambient air.
A load of 0 m2 was applied and left as it was. After 24 hours, the sample was taken out, and it was qualitatively determined whether the cut adhesive surface had recombined.

The evaluation was as follows: ○ if recombination was not observed, △ if slight recombination was observed, and × if recombination was clearly observed.

According to J Engineering 19 DO205, an accelerated light test was conducted on the sample using a Sunshine Carbon Weatherometer. The glaze layer surface of the sample began to fade after being irradiated for 10 hours, and the degree of discoloration was determined as follows.

O: Almost no yellowing ×: Yellowing \”,,,, \2, Note) 2-xw: 2-ethylhexyl acrylate B A: Butyl acrylate
: Acrylic acid MA: Methacrylic acid GMA: Dalicidyl methacrylate MM: Methyl methacrylate Bt: Styrene 2-xHTa: 2-ethylhexythioglycolate!
: Ethylene vAa: Vinyl Ik acid Vat : Vinyl chloride DOM : Dioctyl maleate VtxoT
hiQ: Peoba 10 (product name of Shell Chemical Co., Ltd.)
! A: Ethyl acrylate DAM:
Diaryl! As is clear from the rate test results, when the φ) component is not mixed, as shown in Comparative Example 1,
The adhesion is insufficient and the lance is poor.

Among components (A), α, β unsaturated carboxylic acid or 1 has insufficient cohesive force as shown in Comparative Examples 2 to B, if either one of the epoxy group-containing monomers is missing. The balance of adhesive strength is poor and the adhesive is difficult to cut.

When ethylene-vinyl acetate di-containing conjugate emulsion carbonate is used as component (B), the light resistance is poor as in Comparative Example 4. On the other hand, Examples 1-11 have poor adhesive performance (lance, glue, etc.). It can be seen that it is excellent in all aspects, including cutting and light resistance.

Patent Applicant Hoechst Synthetic Co., Ltd. Procedural Amendment (Item 1 April 22, 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono 1 Indication of the case 1982 Patent Application No. 242728 2 Name of the invention Excellent light resistance Emulsion-type pressure-sensitive welding *Relationship with the case of the person who makes the third amendment Subject of the patent applicant's fifth amendment (1) Contents of the amendment in column six of the "Claims" of Akira (1) The description of the " ``Scope of Claims'' is amended as shown in Appendix ``Amended Claim 41.''

7 Attachments 1. Catalog of Classifications (1) Amended Claims I A light-resistant emulsion type pressure-sensitive adhesive made by mixing.

(ii) Acrylic acid ester and (overlapping) methacrylic acid ester monomer having an alkyl group having 4 to 12 carbon atoms 50 to 99,7
jlf 臘% (b) Copolymerizable monomer consisting of α, β unsaturated carboxylic acid 0.2 to 15% (c) Copolymerizable monomer containing epoxy group 0.
1iSiI As a cedar fraction: 40-95 heavy weight (Bl←) ethylene-carboxylic vinyl ester-acrylic ester and/or methacrylic acid "X-tyl co-x combination emuldimine, ethylene-carboxylic vinyl ester-vinyl chloride copolymer Combined emulsion, ethylene-
At least one type of vinyl acetate-higher carboxylic acid vinyl ester copolymer having 5 to 12 carbon atoms and (
or) (b) Ethylene-vinyl acetate copolymer emulsion, ethylene-vinyl carboxylate ester-vinyl chloride copolymer emulsion, ethylene-vinyl acetate-carbon number 5-1
One or more acrylic modified ethylene copolymer emulsions obtained by two-stage polymerization of an acrylic ester and/or a methacrylic ester to at least one of the higher carbon vinyl ester coelectric polymer emulsion described in No. 2. copolymer emulsion with a solid content of 60~
5 parts by weight (0) Acrylic ester and (t) or methacrylic ester having a furkyl group having 4 to 120 carbon atoms, dialkyl maleate and (or) dialkyl maleate, carboxylic acid vinyl ester, and optionally a functional group. An acrylic-unsaturated dibasic acid diester copolymer produced by copolymerizing a monomer having the following and/or a monomer having two or more double bonds! 0 to somit portions of solid content.

2 The copolymerizable monomer consisting of a, β-unsaturated carboxylic acid in 1(A)(b) is acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and its halfester, hexamaric acid and its The light-resistant emulsion-type pressure-sensitive adhesive according to claim 1, which is at least one cypress selected from Hafestel.

31. The light resistance according to claim 1, wherein the epoxy group-containing co-merging monomer of 31(A) and (c) is an unsaturated acid glycidyl ester and/or unsaturated glycidyl ether monomer. Emulsion type pressure sensitive adhesive.

4. The ethylene-vinyl acetate iron/blood combination emulsion of 1(B) is an ethylene-vinyl acetate basic combination with an ethylene content of 5 to 501 L. Claims 1, 2, or 6 A light-resistant emulsion-type pressure-sensitive adhesive as described in .

51(B) (a) Ethylene-carboxylic acid vinyl ester-acrylic ester and (or methacrylic ester) co-electrolyte composite!
50% by weight, carboxylic acid vinyl ester! IO~85
The light resistance according to claim 1, 2, @5, or 4, which is a copolymer emulsion containing 10 to 85% by weight of an acid ester and/or a methacrylic ester of 5 to 50% by weight. Emulsion type pressure sensitive adhesive.

61 (B) fO and (B) ethylene-carboxylic acid vinyl ester-vinyl chloride comonomer! The emulsion contains 10 to somt% ethylene and vinyl carboxylic acid ester! Claims 1 and 2, wherein the agglomerated vinyl is a copolymer emulsion with a weight of 5 to 50%.
6. The light-resistant emulsion type pressure sensitive adhesive according to item 6, item 4, or item 5.

7 1 (B) K) and (B) ethylene-vinyl acetate-charcoal ges~12 higher carboxylic acid vinyl ester co-electropolymer emulsion contains 10 to 50% by weight of ethylene and 30 to 85% by weight of vinyl acetate. Claims 1, 2, and 3r are copolymer emulsions containing 5 to 50% by weight of higher carboxylic acid vinyl esters having 5 to 12 carbon atoms.
ji, the light-resistant emulsion type pressure-sensitive adhesive according to item 4, item 5, or item 6.

In the acrylic-unsaturated dibasic acid diester copolymer emulsion of 81(0), the acrylic ester and/or methacrylic ester monomer is 65 to 65% by weight based on the total monomers. Range 1st term,
The light-resistant emulsion type pressure-sensitive adhesive according to item 2, item 6, item 4rJ1, item 5, item 6, or item 7.

9 Acrylic-unsaturated dibasic acid diester M of 1(a)
In the copolymer emulsion, dialkyl maleate and/or difurkyl 7! The rate monomer is 15 to 65*ii% of the total monomer + THil range 1st term, 2nd term, 3rd term, 4th term, 5th term, 6th term, The light-resistant emulsion pressure-sensitive adhesive according to item 7f or item 8.

10 1(0) 7cryl monounsaturated dibasic acid diester copolymer! Claims 1, 2, 11, 4, and 5J in which the carboxylic acid vinyl ester monomer is present in an amount of 15 to 40% by weight based on the total monomers.
J, acrylic-unsaturated dibasic acid diester copolymer emulsion bag of light-resistant emulsion-proof pressure sensitive adhesive 0 11 1(0) as described in Item 6, Item 7, Item 8 or Item 9 Claims 1 and 2, wherein the monomer having a functional group and/or the monomer having two or more double bonds is 0 to 5.0% by weight based on the total monomers. 2nd term, 6th term, 4th term, 5th term, 6th term,
The light-resistant emulsion-free pressure sensitive adhesive according to item 7, 8, 9 or 10.

12 A light-resistant emulsion wrinkle pressure-sensitive adhesive made by mixing the following (A), P), and (0).

(M')k) Acrylic acid ester and (or) methacrylic acid ester monomer group having an alkyl group having 4 to 12 carbon atoms ~99.7M*% (b) a, β
Consisting of unsaturated carboxylic acid 0.2-15mm%
Copolymerizable monocap (c) Copolymerizable monomer containing epoxy group 0.1
Acrylic yarn obtained by emulsion polymerization of a monomer mixture consisting of 0 to 501L in the presence of a chain transfer agent. 40 to 95 weight doctor (
B) (a) Ethylene-carboxylic acid vinyl ester-acrylic ester and/or methacrylic ester copolymer emulsion 1 Ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer emulsion, ethylene-
At least one type of high carboxylic acid vinyl ester copolymer emulsion having 5 to 12 carbon atoms and (
or) (b) Ethylene-vinyl acetate co-enriched emulsion, ethylene-carboxylic vinyl ester-vinyl chloride co-enriched emulsion, ethylene-vinyl acetate-carbon number 5-1
2 higher carboxylic acid vinyl ester co-enriched polymer-)
One or more copolymer emulsions released from an acrylic modified ethylene copolymer emulsion obtained by two-stage polymerization of an acrylic ester and/or a methacrylic ester in at least one type of Elin, in solid content.
60 to 5 parts by weight (0) Acrylic ester and (or) methacrylic ester having a furkyl group having 4 to 12 carbon atoms, dialkyl 7-late and (or) dialkyl 7-malate, carboxylic acid vinyl ester, and optionally Acrylic-unsaturated dibasic acid diester copolymer emulsion obtained by copolymerizing a monomer having a functional group and/or a monomer having two or more double bonds, with a solid content of 0 to 50 Claims: The chain transfer agent in the weight part 01612 (I) is a chain transfer agent having a chain transfer constant to styrene of 0.01 or more, and is used in a proportion of 0.01 to 10% by weight based on the total monomers. 13. The light-resistant emulsion wrinkle pressure sensitive adhesive according to item 12.

14 The copolymerizable monomer consisting of a, β-unsaturated carboxylic acid of 12 <ixa> is selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and its hafester, 7marl and its hafester. Claim 12 or 1 which is at least one person
I1 Kisoft's light resistance work! Lujon grip pressure sensitive adhesive.

Claims 12, 16, or Light-resistant emulsion wrinkle pressure sensitive adhesive described in item 14 016 12 (B) 1 m)
Claims 12, 16, 1, wherein the ethylene-vinyl acetate copolymer emulsion is an ethylene-vinyl acetate copolymer having an ethylene content of 5 to 50% by weight.
The light-resistant emulsion described in item 4 or item 15 is used as a pressure-sensitive layer agent.

17 12 (B) Ethylene-carboxylic vinyl ester-acrylic ester and/or stellate of (A) is '60-8560-85% by weight acid ester and (
or) a copolymer emulsion containing 5 to 50% by weight of methacrylic acid ester, Claim 12, Claim 1
The light-resistant emulsion type pressure-sensitive adhesive according to item 6, item 14, item 15, or item 16g1.

18 12@) (a) and (a) The ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer emulsion contains 10 to 50% by weight of ethylene, the carboxylic acid vinyl ester has an ISO to 85% weight range, and the salt weight is Claim 1 which is a copolymer emulsion of 5 to 50% by weight
2nd term, 16th term, 14th term, #! Light-resistant emulsion type pressure-sensitive adhesive according to item 15, item 16 or item 17 0 19 12 (B) (() and (b) ethylene-vinyl acetate-higher carboxylic vinyl ester having 5 to 12 carbon atoms) Kyodo Gosai Ko Marujiken contains 10 to 50% by weight of ethylene and 60 to 85% by weight of vinyl acetate - 5 and 5 to 12 carbon atoms.
Special #! which is a copolymer emulsion containing 5 to 50% by weight of higher carboxylic acid vinyl ester! F##Search range 12th
Section 16, Section 14, Section 15, Section 16, Section 17
The light-resistant emulsion-type pressure-sensitive m-adhesive according to item 1 or item 18.

20 In the acrylic-unsaturated dibasic acid diester copolymer emulsion bath of 12(Q), acrylic ester and/or methacrylic ester monomer is present in an amount of 65 to 65% based on the total monomers. A light-resistant emulsion type pressure sensitive adhesive according to certain claims 12, 15, 14, 15, 16, 17, 18, or 19.

21 A patent claim in which the acrylic-unsaturated dibasic acid diester copolymer emulsion of 12(0) contains dialkyl maleate and/or dialkyl hepta-maleate in an amount of 15 to 65% by weight based on the total monomers. range jlH2 term, 16th term, 14th term, 15th term, 16th term
j1, the light-resistant emulsion type pressure-sensitive adhesive according to item 17, item 18Jl, item 19 or item 20.

22 12(0) acrylic double saturated 2111 group acid diester yarn co-polymerized emulsion carbon, wherein the carboxylic acid vinyl ester monomer is 15 to 40% by weight based on the total monomers. 12. The light-resistant emulsion type pressure-sensitive adhesive according to item 12, item 16, item 14, item 1s, item 16, item 17, item 18, item 19, item 20, or item 21.

25 12 (0) In the acrylic two-year saturated diester acid diester thread copolymer emulsion, monomers having functional groups and/or monomers having two or more two-point bonds are present in all jlt polymers. Claims J112, 16, 14, and 15 have a range of 0 to 5,0
Section 16, Section 17, Section 18, Section 19, Section 20
Light-resistant emulsion-based pressure-sensitive adhesive according to item 1, 21 or 22

Claims (1)

[Claims] 1. The following (4) and O! A light-resistant emulsion type pressure-sensitive adhesive obtained by mixing l) and (0). η) (a) Acrylic ester and (or) methacrylic ester monomer 5N 9.7% by weight (b) α,
Copolymerizable monomer bottled from β-unsaturated carboxyl alcohol (3) Copolymerizable monomer containing epoxy groups 0.1-5
．． 0% by weight) other monomers copolymerized with the above monomers 0~
The solid content is an acrylic copolymer emulsion obtained by emulsion polymerization of a monomer mixture consisting of 50% by weight.
4N15 parts by weight CB) Gn ethylene-carboxylic acid vinyl ester-acrylic ester and/or methacrylic ester copolymer emulsion, ethylene-carbonyl vinyl ester-vinyl copolymer emulsion, ethylene-
At least one pole of vinyl acetate-vinyl ester copolymer emulsion of vinyl acetate-charcoal 3 & FIN12 and (or) ethylene-vinyl acetate copolymer emulsion, ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer Emulsion, ethylene-vinyl acetate-carbon In-12
1 or 2 pieces of acrylic modified ethylene yarn co-polymer emulsion obtained by two-stage polymerization of acrylic acid ester and/or methacrylic acid ester to at least one type of high-grade carphone-dispersed vinyl ester co-polymer emulsion.
Copolymer emulsion with a solid content of 60 to 5
Bulky part (0) acrylic ester and (J or) methacrylic loose ester having an alkyl group having 4 to 12 carbon atoms, dialkyl maley Y and (or) dialkyl 7 maleate, and carboxylic acid vinyl ester. One type of acrylic double-handed saturated dibasic acid diester thread copolymer emulsion obtained by copolymerizing a monomer having a single functional group and/or a monomer having two or more double bonds, if desired. 80 parts by weight per minute. 21 (4) IP) are acrylic acid, ita methacrylate, conic acid, tarotonic acid, maleic acid, and ("El) Hafestel, 7 malic acid. The light-resistant emulsion-type pressure-sensitive adhesive according to claim 1, which is at least one type different from 61 (A) and Hafestel. , an unsaturated acid glycidyl ester and/or an unsaturated glycidyl ether monomer - the light-resistant emulsion type pressure-sensitive skin contact agent according to claim 1. The light-resistant emulsion type sensitive layer according to claim 1, 2, or 6, wherein the vinyl copolymer emulsion is an ethylene-vinyl acetate copolymer with an ethylene content of 14. (B) The ethylene-carboxylic vinyl ester-acrylic transparent ester and/or methacrylic transparent ester copolymer emuldigon of (a) contains ethylene of 10-5
0 mu wrinkle%, calphonium vinyl ester is 3H5] 11L
The light-resistant emulsion according to Claims 1 and 2, XJs Item 6 or 4, which is a copolymer emulsion containing 5 to 50 m% of acrylic ester and/or methacrylic ester Type arbitrary pressure contact layer agent. The ethylene-carboxylic acid vinyl ester-vinyl chloride co-polymerized emulsion of 61(B) (A) and 1) contains 110-503k1% of ethylene, 50-J85% of vinyl chloride, and s5-1o of vinyl chloride. The light-resistant emulsion-type pressure-sensitive adhesive according to claim 1, 2, 6, 14, or wSb, which is a copolymer emulsion of Arashi%. 71(B) (a) and (b) ethylene-6n, rH
Vinyl - carbon 11! y-12 sieve grade carboxylic acid vinyl ester co-ester polymer emulsion, ethylene is 10A-5
0M-%%tnM vinyl 60-85 weight attack, carbon H2
Claims 1 and 2 are copolymer emulsions of 5 to 50 higher carboxylic acid vinyl esters.
A light-resistant emulsion sensitive adhesive according to item 5, item 5XA, item 4, item 5 or item 6. In the 61(0) acrylic ester and/or methacrylic acid ester monomer in the acrylic ester and/or methacrylic ester monomer in an amount of 66-45% by weight based on the total monomers, The yoke of a certain shattered liver w5 Section 1 Section 1 Section 2, Section 6 Section 4, Section 5, Section 6 or Section 7
A light-resistant emulsion gripping pressure-sensitive adhesive as described in . Kill 7 malate monomer is 15-651 based on total monomers
Claims 1, 2 and 6 are
10 1 (0) acrylic saturated two-salt mackerel In the string diester yarn co-mercury emulsion, the carboxylic acid vinyl ester monofilament has an i 5-40 rich IIk% based on the total monomers.
The range of claims for the pin pins: 1st, 2nd, 6th, 4th, 5th, ! ! Item 6\Light-resistant emulsion type pressure sensitive adhesive according to Item 7, Item 8 or Item 9. 11 In the acrylic-unsaturated 2-base diester yarn co-enriched emulsion of 1(0), the body having a blind group and/or the single body having 2 or more of A needle that burns the body and has a critical condition of θ~5.0% Claims No. 1, No. 2, No. 6 Jlj! , 4th box 1, 5th box 1
6th D to Section 7, Section 8, Section 9 JJI or Section 10) Resistant type feeling) i. Closed wound. (lId) Acrylic loose Nisder and/or methacrylic varnish fk having an alkyl group having 4 to 12 carbon atoms
Single porcelain body 60-99.7 true j1% IP) α
, a 0.2-15 cliff consisting of β-unsaturated carboxylic acid
Monolithic polymer (c) Co-polymerized polymer containing epoxy group o, vol. 4
．． o Megumi) Other monomers that resonate with the above monomers 4
00% by weight of an acrylic copolymer emulsion obtained by emulsion polymerization in the presence of a continuous transfer IELL agent. Co-emulsion of vinyl ester-acrylic ester and methacrylic powder, ethylene-carboxylic vinyl ester-vinyl chloride emulsion, ethylene-vinyl acetate-
At least one type of higher calphone vague vinyl ester copolymer emulsion having a carbon number of H2 and (or) a trunk 1 ethylene-vinyl vinegar co-polymer emulsion, ethylene-cardanoic acid vinyl ester-vinyl chloride copolymer emulsion, ethylene vinyl ester Acrylic string esthetics Mizuyohi (
or) 1 portion of a copolymer emulsion with 1 or more strands selected from acrylic ethylene thread copolymer emulsion obtained by two-stage polymerization of methacrylic acid ester 6
Acrylic ester and (or) methacrylic ester having an alkyl group having 0 to 5 gravimetric heat (0) carbon atoms, dialkyl maleate and (or) dialkyl 7-maleate, calphonic vinyl ester, and optionally ゛B Acrylic saturated 2 to 2-based diester yarn symbiotic emulsion selected by copolymerizing a monomer having the ability Ak and (or) a monomer having 2 or more bonds in LMj min. 0-J50 books-9. 164 to f# cedar cutting or styrene is a transfer agent with a σ11 cherry blossom constant of 0.01 or more, and is used in a proportion of 0.01-10% for the whole car body. Range 123rd
A light-resistant emulsion adhesive according to J. Copolymerizable monomers consisting of α, β unsaturated carboxylic acids of 14 12fitP) were carried from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and their hafester, fumaric acid and its 8-7 esters. At least one light-resistant emulsion type pressure-sensitive adhesive according to claim 1 or 1-4. 1512AH' The copolymerizable monomer containing an epoxy group is an unsaturated acid glycidyl ester and/or unsaturated glycidyl ether monomer, Claim 1, Item 16 or 14 The light-resistant emulsion type pressure-sensitive adhesive described. The ethylene-vinyl acetate copolymer emulsion of 161 or Naka) has an ethylene content of 1NO weight arc.
Claim II, which is a vinyl acetate copolymer,
The ethylene-carboxylic acid vinyl ester-acrylic ester and/or methacrylic ester copolymer emulsion of the light-resistant emul p 1712 (B) (a) according to item 16, item 14, or item 15, ethylene is 1
80% by weight, carboxylic acid vinyl ester is 6 N5 weight 1
%, acrylic ester and/or methacrylic ester are copolymer emulsions containing 5-40% by weight of claims 10, 13, 14, and 15.
The light-resistant emulsion type pressure-sensitive adhesive according to item 1 or 16. 181'21B) &) The ethylene-carboxylic acid vinyl ester-vinyl chloride copolymer emulsion of (a) and (b) contains 180% by weight of ethylene, 5% by weight of carboxylic acid vinyl ester, and 5-60% by weight of vinyl chloride. % copolymer emulsion according to claim 12, 15, 14, 15, 16 or 17. 1916) &) and (b) ethylene-vinyl acetate-
The emulsion of a high carboxylic acid vinyl ester copolymer having 5 to 12 carbon atoms contains 1N0 weight of ethylene, 50 to 85 weight of vinyl acetate, and 5 to 50 weight of higher carboxylic acid vinyl ester having 5 to 12 carbon atoms. The light-resistant emulsion type pressure sensitive coating according to claim 112, 1δ, 14, 111, 16, 17, or 18, which is a copolymer engineered resin. glue. 2012 (0), in which the acrylic ester and/or methacrylic ester monomer is 686% by weight based on the total monomers in the acrylic-unsaturated dibasic acid diester copolymer emulsion film. A light-resistant emulsion carbon layer pressure-sensitive adhesive according to item 12, item 16, item 14, item 15, item 16, item 17, item 18, or item 19. In the former 12 (0) acrylic-unsaturated dibasic acid diester copolymer emulsion, the dialkyl maleate and/or dialkyl 7-maleate monomer is 1 to 5 based on the total monomers. Claims 12, 16, 14, wS15, 1 which are weight %
The light-resistant emulsion type pressure sensitive adhesive according to item 6, item 17, item 18, item 19 or item 20. In the acrylic dibasic acid diester M copolymer emulsion of 2212(0), the carboxylic acid vinyl ester monomer is 16-40% by weight based on the total monomers. Light-resistant emulsion type pressure-sensitive adhesive according to item 12, item 15, item 14, item 15, item 16, item 17, item 18, item 19, item 20, or item 21. agent. In the acrylic-unsaturated dibasic acid diester copolymer emulsion of 261 Claims 12, 16, 14, 15rJl, @1 which are .0% by weight
6m, Section 17, Section 18, Section 19, Section 20, Section 2
Light-resistant emulsion gripping pressure-sensitive adhesive according to item 1 or item 22