JPH05504992A - Poly(vinyl chloride) copolymer lamination adhesive - Google Patents

Abstract

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

Description

[Detailed description of the invention] Polyvinyl copolymer Qi Once Jυ”1 Technique J Takuyachu The present invention relates to adhesives used for adhering laminates. In particular, poly(vinyl alcohol) poly[vinyl chloride and/or vinylidene] copolymer of the species consisting of Aqueous dispersions of mer are suitable for use with low-energy, hard-to-adhere materials such as plasticized poly(vinyl chloride). Particularly suitable as a surface adhesive.

Brother's JL amount Aqueous polymer dispersions or latexes made from vinyl monomers are Used as adhesive in various fields such as adhesives, pastes, paints and coatings. came. plasticized poly(vinyl chloride), certain other polymer supports, glass or Gold 11! Obtained when used with adhesives for low-energy, hard-to-adhere surfaces such as foils. The results are often unsatisfactory. Plasticized poly(salt) is a low energy adhesion support. (vinyl chloride) poses a particular challenge. Soft poly(vinyl chloride) film is a decorative wall panel. A wide range of products such as flannel, furniture veneer, luggage, and various laminates with different supports. Used in many industrial applications. Usually used to soften poly(vinyl chloride) film Large amounts of plasticizers are used. In general, plasticizers such as phthalates, especially A migratory substance that has a tendency to leach from poly(vinyl chloride) into the adhesive upon aging. It is. This migration weakens the adhesive and even destroys the nucleating agent to the point that it cannot adhere.

Poly(vinyl acetate) homopolymer dispersions are characterized by their rapid curing speed, polymer strength, and is often used as an adhesive because of its ability to adhere to difficult-to-adhere surfaces. deer However, poly(vinyl acetate) is a rigid polymer at ambient temperatures. Poly The hardness of the mer generally reduces bond strength. Good adhesion to this difficult-to-adhere surface Addition of plasticizers to the polymer is required to obtain properties. Poly(vinyl acetate) Plasticizers used in weaken the layer and make it useless.

Overcoming the problems of stiffness of poly(vinyl acetate) and weakening of the adhesive layer due to plasticizer migration In order to Copolymers with soft monomers such as tel were developed. This polymer emulsion Comonomers used in polymer polymers often introduce ester side groups, thereby , the flexibility of the polymer is increased by allowing intra- and intermolecular movement. . This comonomer is described as an "internally" plasticized poly(vinyl acetate).

A soft comonomer that acts as an internal plasticizer binds to the polymer chain and prevents migration or make it difficult to suffer from the disadvantages of This permanently plasticized copolymer is more , showing generally high adhesion to plastic surfaces, probably because the softer copolymer associated with the ability to deform or wet the non-porous surface of a plastic film. Ru. However, in many applications, plasticizers are used as one of the ingredients in adhesive formulations. used. The adhesive layer of this copolymer weakens when in contact with plasticizers. For example, in addition to aqueous polymer dispersions, adhesive formulations often contain plasticizers, solvents, Contains other ingredients such as thickeners, fillers and additives for special end-use properties. Ru. Plasticizers used in adhesive formulations make poly(vinyl acetate) copolymers more It has a tendency to soften and weaken the adhesive layer. Furthermore, this copolymer adhesive and Upon contact with plasticized poly(vinyl chloride), the plasticizer in the poly(vinyl chloride) ages It tends to transfer to the adhesive layer and cause the layer to lose its adhesion.

Development of vinyl acetate-ethylene copolymer enables low-energy adhesive bonding on surfaces that are difficult to adhere to. The adhesion properties of the conventional poly(vinyl acetate) copolymers were further improved. ethylene Like other soft comonomers, it functions as an efficient internal plasticizer. in general, Vinyl acetate-ethylene copolymer is probably (vinyl acetate-ethylene copolymer) Due to better polar interaction with low energy surface adhesion supports, conventional poly( In addition, this latex exhibits better adhesive strength than vinyl acetate) copolymers. Adding appropriate amount of external plasticizer does not affect the peel strength of the laminate, vinyl acetate - Lamination of other supports to plasticized poly(vinyl chloride) using ethylene copolymers When aged, the adhesion of the laminate shows little change with aging.

Ar from Air Products and Chemicals Inc. Aqueous polymer dispersions of vinyl acetate-ethylene copolymers such as RFLEX@400 The body has an alternative conventional poly(vinyl acetate) copolymer that supports low energy surface adhesion. It is touted as an adhesive emulsion for workhorses for laminating supports. (1,5 keist ill collection,”) Iandbook of Adhes ives-1 2nd edition, Van No5trand Re1nhold Comp Any, New York.

1977, p. 484-494), the product contains such vinyl acetate. - U.S. Patent No. 3 for Batch Preparation and Utilization of Ethylene Copolymer Emulsions , No. 708.388 Specification 1. Vinyl acetate-ethylene copolymer A continuous method for making emulsions is described in U.S. Pat. No. 4,164,489. It is listed. Higher solids vinyl acetate-ethylene copolymer emulsion The invention is described in European Patent Application No. 279,384.

Aqueous polymer dispersions of vinyl acetate-ethylene copolymers can be produced in several ways. For example, ethylene is a gas at normal temperature and pressure, and cannot be stored in a cryogenic tank. Ethylene transfer to one reactor usually requires a compressor and is therefore easy to transfer in winter. Avoid critical conditions of low temperature and high pressure, such as temperatures reaching 9°C, which may damage the transfer equipment. Care must be taken not to create a solid-gas coexistence state in the boundary zone. Ethylene does not co-react with vinyl acetate in emulsion polymerization except under high pressure; Therefore, the reaction vessel must have a considerable wall thickness in order to withstand the high working pressures well. Therefore, heat removal using reactor jacket cooling is inefficient due to the substantial wall thickness. Extremely low. Expensive external circulation designed for full reactor pressure for maximum heat transfer A ring heat exchanger is generally required. In addition, circulation pumps, seals, valves and piping It should also be able to withstand elevated pressures well. Thus, such reactor systems have virtually no However, larger investments are required. The work and maintenance costs of such high-pressure reactors are also Also quite expensive.

Copolymers of vinyl chloride and other monomers are used in adhesives and other fields. For example, U.S. Pat. No. 4,189,415 to Eck et al. Aqueous salts containing poly(vinyl chloride) as protective colloids in adhesive applications A vinyl chloride/vinyl acetate/ethylene copolymer dispersion is described. Also, Ia Coviello European Patent Application Publication No. 0.206,295 Poly(vinyl chloride) stabilized vinyl chloride/ethylene copolymer emulsion useful for coating The version is listed. These ethylene-based copolymers require high working pressures and large Similar to the previously mentioned vinyl acetate/ethylene copolymer, it requires a large amount of investment and is difficult to manufacture. There are restrictions.

However, water-based polymers are easy to manufacture and are effective adhesives for hard-to-adhere surfaces. - I have a lot of needs for my limbs! j The present invention relates to an adhesive, a method for laminating materials, and a laminate made using the adhesive. . The adhesive composition comprises water, poly(vinyl chloride) and an effective adhesive amount of poly(vinyl chloride). aqueous dispersion containing vinylidene copolymer and/or vinylidene copolymer. (a) about 5 to 70% by weight of vinyl chloride or vinylidene chloride, (b) 1 about 30-95% by weight of one or more ethylenically unsaturated carboxylates and (C) other Repeating units consisting essentially of less than about 5% by weight of ethylenically unsaturated monomers Ru. The laminate comprises an adhesive composition comprising - one or more layers to be laminated together and/or produced by applying to the surface of a support material and then laminating the materials together .

color supervisor lj Poly(vinyl alcohol) stabilized poly[vinyl chloride and (also) vinylidenko] Copolymer dispersions can be used on glass, plywood, metal foil and plasticized poly(vinyl chloride) fibres. Excellent adhesion to a variety of substrates, including low-energy, hard-to-adhere substrates such as It was discovered that it was an adhesive. This adhesive has excellent freeze-thaw stability, mechanical stability, Faster curing speed, better release time and better wetting customization on various substrates This adhesive also incorporates ingredients such as solvents and plasticizers into the adhesive formulation. It has sufficient tolerance to Adhesive strength is generally increased by adding plasticizers. maintained or enhanced. Plasticized poly(vinyl chloride) on different materials using the adhesive. nucleating agent causes an abnormally high adhesion force in the early stages of adhesion. 0 strong adhesion, retained even after aging. Additionally, the adhesive is relatively warm. The working pressure during the zero reaction, which can be prepared under mild conditions and low pressure, is This is only about one-tenth of the working pressure for ethylene polymerization. Thus, the manufacturing equipment The investment and operating or maintenance costs associated with vinyl acetate-ethylene copolymer significantly lower than that of the dispersion.

Aqueous dispersions useful as adhesives of the present invention generally include vinyl chloride or chlorofluorene. tyrene, or vinylidene chloride or 1,1-dichloroethylene, or both. Manufactured by combining. Vinyl chloride is preferred.

The type of comonomer copolymerized with vinyl chloride and/or vinylidene monomer is Less critical, any suitable ethylenically unsaturated carboxylate and optionally 0 representative ethylenically unsaturated carboxylic acids that can be selected from other addition monomers Rate comonomers include, but are not limited to, one or more of the following compounds: Vinyl pionate, vinyl formate, vinyl n-butyrate, vinyl alcohol (vers atate), vinyl laurate, vinyl stearate, vinyl pivalate, 2 - Vinyl carboxylate such as vinyl ethylhexanoate; acrylic acid n- Butyl, isobutyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate Sil, acrylic oleyl, dodecyl acrylate, stearyl acrylate, male Di-2-ethylhexyl inoate, di-2-ethylhexyl fumarate, maleic acid Dimethyl, dimethyl fumarate, di-n-butyl maleate, di-n-butyl fumarate Acrylates such as diethyl maleate, diethyl fumarate, etc. and hyfumarate, other representative addition monomers include, but are not limited to, acrylic acid, Tacrylic acid, sodium vinyl sulfonate, acrylamide, methacrylamide , sodium 2-acrylamido-2-methylpropanesulfonate (AMPS■ ), diacetone acrylamide, N-methylolacrylamide, N-methylol methacrylamide, maleic acid, fumaric acid, itaconic acid, crotonic acid, 1.4 -butanediol acrylate, l.

4-Butanediol dimethacrylate, diallyl maleate, diviny adipate vinyl crotonate, pentaerythritol triacrylate, diaryl adipate triallyl cyanurate, triallyl isocyanurate, hydroxy acrylate One or more of ethyl, hydroxypropyl acrylate, etc. are included. Preferred d Thyrenically unsaturated carboxylates include vinyl acetate, □-butyl acrylate, and acrylate. other preferred comonomers include triallyl cyanurate, vinyl crotonate, and N-methylolacrylamide.

Vinyl chloride and/or vinylidene used, ethylenically unsaturated carboxy The rate and relative amounts of other comonomers are less critical; generally, vinyl chloride The amount of vinylidene and/or vinylidene is about 5% to 70% by weight based on the weight of total monomers. Preferably it ranges from about 1 to 70% by weight, most preferably from about 10 to 35% by weight. one Generally, the amount of ethylenically unsaturated carboxylate is about 5-95% by weight, preferably about The range is 10-70% by weight, most preferably about 65-90% by weight. One or more types of When using thyrenically unsaturated carboxylates, the amount of comonomer used is For example, vinyl carboxylates generally have a It ranges from 10 to 70% by weight, preferably about 20 to 50% by weight. Acrylic acid, ma The amount of leic acid and fumarate comonomer used is generally about 10-70% by weight. Preferably it is in the range of about 20-60% by weight. Amounts of any other comonomers used is generally less than about 5% by weight, preferably less than about 5% by weight, and preferably less than about 1% by weight. It is full.

Any suitable polymerization method can be used, such as emulsion. The method is half-time It may be a fractional method, a stepwise adiabatic method, a batch method, a continuous method or any other suitable method. .

Any suitable polymerization conditions can be used. Generally, the temperature is about 0-100°C. Preferably, the temperature range is about 40 to 90°C, and the pressure is about 1 to 10 atm, preferably about 3 to 8 atm. atmospheric pressure range.

Polymerization can be carried out using a polymerization initiator, preferably a nucleating agent. It will be done. Suitable polymerization initiators include, without limitation, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydrogen peroxide, di-t-butyl peroxide peracetic acid, perbenzoic acid, diacetyl peroxide, t-butyl peracetate, perbenzoic acid Water-soluble peroxides that generate free radicals such as t-butyl and 2.2°-azobyl Included are azo initiators such as suisobutyronitrile and the like. of such free radical initiators. The amount used generally ranges from about 0.05 to 6% by weight based on the weight of monomer. With another method and especially when carrying out the polymerization at lower temperatures, the use of redox initiators For example, a reducing agent can be used in addition to the peroxide initiator described above. 0 Representative reducing agents include, but are not limited to, alkali metal bisulfites, sulfoxylates, salts, thiosulfates, sulfites, bisulfites, reducing sugars such as glucose, sorbate Ascorbic acid, erythorbic acid and the like are included.

Generally, the reducing agent is used at a level of about 0.01 to 6% by weight based on the weight of the monomer. Ru.

Polymerization is carried out in the presence of stabilizers or protective colloids of the aqueous polymer dispersion.

Generally, poly(vinyl alcohol) is preferred, but ELVANQL and Named E, 1. DuPont de Nemours & (:company Any suitable stabilizer or copolymer, such as poly(vinyl alcohol) manufactured by Co., Ltd., Inc. Lloyd can be used. Stabilizers add wet tack or quick fixation to aqueous polymer dispersions. Poly(vinylvinyl alcohol) suitable for use in the present invention provides desirable adhesion properties such as fast cure speeds. alcohol) is generally about 70 to 90 mol%, preferably about 84 to 89 mol% is partially hydrolyzed and has a degree of polymerization ranging from about 100 to 4000. Also, complete Totally hydrolyzed poly(vinyl alcohol) can also be used. The stabilizer is can be added to aqueous polymer dispersions after polymerization; It is preferred to add stabilizers during the polymerization to obtain better stability.

Various additives can be cured before polymerization or added during or after polymerization. I can do it. These additives include surfactants, buffers, neutralizers, defoamers, and chain transfer. agents and plasticizers. Suitable surfactants that may be used include alkyl and (or) Aryl sulfates, sulfonates or carboxylates such as lauryl sulfate Sodium acid, sodium alkylaryl polyether sulfate, etc. Kylated fatty amines, fatty acid amides and/or monoalkylphenols such as Oxyethylated lauryl alcohol, oxyethylated oleyl alcohol, ethylated stearyl alcohol, oxyethylated stearamide, oxyethyl oleylamide, oxyethylated p-yneoctylphenol, oxyethyl p-n-nonylphenol, oxyethylated p-n-dodecylphenol, etc. One or more of these are included. As a preferred surfactant, Union Carbi deChemicals and Plastics Company Inc. 15 moles of nonylphenol such as TERGITOL NP-15 from DOWFAX from Xylate and Dot Chemical Company (2) Sodium dodecyl diphenyl oxide such as 2Al is included. surface activity The amount of agent is from 0 to about 15% by weight based on the weight of the monomer, preferably from about 0.5 to 8% by weight. range.

The adhesive of the present invention is compatible with plasticizers. Adding plasticizers often results in lower energy However, as a representative plasticizer, butoxyethyl Cyacetate; acetyl ricinoleic acid butyl ester; oxalic acid, succinic acid, azide Diesters of pinic acid, phthalic acid and aliphatic unbranched or straight-chain alkanols, e.g. Oxalic acid dibutyl ester, succinic acid dibutyl ester, diisotridecyl phthalate , dioctyl phthalate, diisotridecyl phthalate; dipropylene glyco dibenzoate; diethylene glycol dibenzoate: ethylene glyco Propylene glycol: Hexamethylene glycol, diphenylpho Sphate: Triphenyl phosphate; Tricresyl phosphate: Cresi One or more types of diphenyl phosphate and the like are included. V as a preferred plasticizer BENZOF from elsicol Chemical corporatelon Examples include dipropylene glycol dibenzoate such as LEX 9-88.

Plasticizers can be added to the adhesive before, during or after polymerization. plasticizer The amount used is generally less than about 40% by weight based on the weight of the total adhesive composition, preferably from O to Less than about 30% by weight.

A typical emulsion polymerization recipe for preparing adhesive compositions includes water, monomer, and free radicals. Special products such as initiators, protective colloids, emulsifiers, buffers, neutralizers and defoamers Contains reagents as well as any other suitable materials. Water increases the solids content of the adhesive composition by approximately Present in an amount sufficient to provide 40-70% by weight, preferably about 50-65% by weight. .

The adhesive composition consists essentially of water, poly(vinyl alcohol) and an effective adhesive amount of poly(vinyl alcohol). [Comprised of vinyl chloride and/or vinylidene copolymer] effective adhesive amount The poly[vinyl chloride and/or vinylidene copolymer] may contain one or more layers and (or) a sufficient amount of copolymer to adhere the support materials together. general The amount of copolymer is not critical (approximately 5 to 50% based on the total weight of the adhesive composition). 70% by weight preferably in the range of about 1-7% by weight Ru. Also, the amount of stabilizer such as poly(vinyl alcohol) is not too critical. , about 0.1-15% by weight based on the weight of total monomers, preferably about 0.5-10% by weight % most preferably ranges from about 1 to 7% by weight. Adhesive composition used in polymerization Other suitable ingredients other than those listed, such as Ernest W. Flick, Han dbook of Adhesive Raw Materials [Noye from ingredients known in the art, such as those listed in Contains selected ingredients. Other ingredients may be provided in any suitable amounts.

Non-restrictive materials for use with adhesives include plywood, board material, kraft paper, and wood or wood products such as mannite; cloth, canvas and synthetic fibers; woven fabrics such as; metals such as aluminum and steel; glass; leather; (vinyl chloride), polyester, polystyrene, polyethylene, polypropylene and polymethyl methacrylate. One or more of these materials are low energy It consists of hard-to-adhere substances on high-energy or high-energy surfaces. Plastic to such materials Includes polyvinyl chloride, glass, metal foil, etc. Preferably, attach At least one of the materials to be used is a low-energy, hard-to-adhere substance, especially plasticized poly(vinyl chloride). ) or similar difficult-to-adhere materials. Low-energy, difficult-to-adhere substances generally It is difficult to adhere to other substances than other substances, and it is approximately 40 milligiers (mJ)/square meter (Ml ) has a surface energy less than .

The method of applying the adhesive to the layer and/or support material is not critical and is well known in the art. Any suitable method known in the art is included.

Polyvinyl chloride and/or vinylidene copolymers make this a low-energy - Unusually high temperature when used as an adhesive for plasticized poly(vinyl chloride) on difficult-to-adhere surfaces. It is observed that a strong initial adhesion occurs. This high initial adhesion between the adhesive and the adherend This may be due to the stronger physicochemical attraction between the polymer is more compatible with low-energy, difficult-to-adhere surfaces.

The following examples present illustrative embodiments of the invention but are not intended to limit the scope of the invention. Unless otherwise specified, all parts, percentages, and proportions herein, including the claims, refer to Depends on weight.

Medicine” 2: This example demonstrates the use of aqueous polymer dispersions as adhesives for plasticized PVC on various substrates. Figure 2 shows the preparation of the body or latex. Made of 6 steels whose relative amounts of ingredients used are listed in Table I Reaction kettle pressure gauge, stirrer, thermocouple, nitrogen inlet, water jacket and appropriate addition port Deionized water in the amount listed in step A in Table T and E completely dissolved in the water. LvANOL ■50-42 was charged into the pot. In this case, TERGrTOL■ NP-15, D0111FAX■2A1, sodium acetate, NALCO■234 3 (defoaming agent), potassium persulfate, vinyl acetate, vinyl chloride, n-butyl acrylate Chill and acrylic acid were charged in the amounts listed in Step A during surface work. Purge the pot with nitrogen and heated to 67° C. with constant stirring. Vinyl acetate, vinyl chloride, acrylic Butyl acid, acrylic acid and NALCO■2343 in the amounts listed in Step B in Table 1. Added to kettle for 4 hours.

The temperature of the pot was raised and maintained at 75°C. Monitor the pressure in the pot and make sure it is 11. I set it to 00psi or less. After 30 minutes, add potassium persulfate in deionized water. , was added to the kama over a period of 3.5 hours in the amount listed in Step B during the front finishing. added all Afterwards, the temperature of the pot was maintained at 75° C. for 30 minutes or more. ! a small amount of t-butylhydride Residual vinyl chloride was added by adding polyperoxide and sodium metabisulfite as a post-catalyst. lowered to below 10 ppm. The latex was then cooled to room temperature. generation la Tex has a solids content of 54.9% by weight and a viscosity of 3700 cps (Brookfee The spindle was 60 rpm, 25° C.).

Poly(vinyl chloride) or PVC film to plywood, medium density board and mannai The above latex was used as an adhesive to be laminated onto the support. Generally, latex Apply the adhesive using a No. 20 wire-wound applicator to Goodyear Tire & Rub. It was coated onto a plasticized PVC film made by Ber Co+5 pany. This coating P Immediately apply vC film to the top of plywood, medium density board or pine night block. A 4.5 pound roller was passed over the film once. Air the laminate overnight The laminate was then dried or heated in an oven at 60°C for two weeks. The 180° peel strength on lin strips was checked with an Instron. stomach The Instron was set at a crosshead speed of 2 inches/minute on a 10 pound scale.

The results recorded with bond/wire 1n (pli) are shown in Table H. Latex is plywood, medium Good adhesive for plasticized poly(vinyl chloride) on density boards and mannite. It showed good adhesion. Adhesion was well maintained after heat aging.

9-1 This example uses the apparatus described in Example 1 to demonstrate latex preparation by adding plasticizer during polymerization. and procedures were used. First, deionized water, ELVA, in the amounts listed in Step A in Table I NOL■52-22. ELVANOL■51-05, BENZOFLEX■9 -88. TERGITOL■NP-15, DOWFAX■2A1. Sodium acetate NALCO 2343, potassium persulfate, triallyl cyanurate, vinyl acetate A kettle was charged with vinyl, vinyl chloride, butyl acrylate, and acrylic acid. 6 pots When heated to 7°C, vinyl acetate, vinyl chloride, and acetic acid were added in the amounts listed in Step B in Table I. Butyl acrylate, acrylic acid, triallyl cyanurate and NALCO■2343 was added to the reaction kettle over a period of 4 hours. The amount of potassium persulfate supplied and the reaction procedure are as in Example 1. It was the same as that described in . The produced latex had a solids content of 56.0% by weight and 2 Viscosity of 740 cps (Brookfield type LVT, No. 4 spindle, 6 0 rpm, 25°C).

As an adhesive for laminating PvC film to plywood, medium density board and Boblin cotton cloth. The general test method and conditions described in Example 1 using the above latex were used; 0.1 part (7) AEROSOL■0T-75't 5 Texni added, mata To coat latex on PVC film in order to laminate Poblin cotton cloth. 401 using a wire wound applicator. Table H shows the results in bond/line 1n (plf) Describe it in Latex was applied to plasticized PVC films on various supports tested. It showed good adhesion. Adhesion is well retained and even improved after heat aging. Ta.

9-1 This example shows the preparation of latex by post-addition of plasticizer. Its use as a laminating adhesive The performance of a typical high performance commercial vinyl acetate-ethylene copolymer, AirP AIRF products and Che+5icals, Inc. Example 1 Comparison with VAE Designated LEX ■400 The device described in Example 1 was used. example 2 using the procedure and component levels described in Section 2, but with slightly more deionization in the initial charge. water and sodium acetate and triallyl cyanurate as described in Table I. BEZOFLEX 9-88 was removed from the initial charge of Example 2, which was used when supplying. Instead of 0, in this example, 5.0 parts of BEZOFLEX 9-88 is added to the latex. Added later. Prior to plasticizer addition, the resulting latex had a solids content of 53.8% by weight. and 1460 cps viscosity (Brookfield type LVT, No. 4 spindle) , 60 rpm, 25'C).

The above lamination is suitable for laminating PvC film to plywood, medium density board and Boblin cotton fabric. General as described in Example 2 using Tex with 5 parts of BEZOFLEX 9-88 Standard test methods and conditions were used, but in this example no wetting agent was added to the latex. Ta. The performance of latex was compared to commercial VAE. Expressed as bond/wire 1n (pli) The results are shown in Table H. From the results, it was found that the present latex Excellent adhesion as a laminating adhesive for medium density boards and boblin cotton fabrics. It can be seen that this shows that Excellent adhesion was retained even after heat aging. many Adhesion was higher than commercial vinyl acetate-ethylene adhesive emulsions.

The latex was also coated onto kraft paper using a No. 20 wire-wound applicator. straight Place aluminum foil on the coated kraft paper! Aluminum roller and 4.5 pound roller Passed once on foil. We separated the laminate to examine its adhesion strength to aluminum foil, and The failure patterns were investigated after drying the laminates for various periods of time. fibers on kraft paper The fracture pattern with fiber tearing was recognized to have excellent adhesion with aluminum foil. . The results shown below show that this latex has strong adhesion to aluminum foil. shows.

Aluminum foil adhesion to kraft paper 1 11Z Uni latex Ratio H Example 3 Example 3 “VAE’ VAE”’1 Air 7° 9° 11 5 Air 8° 10'' 13 14 50℃ 101 9° 7° 6'''a-1 is the worst, 10 is the best A grade of 1 to 10.

Contains b-5 part BEZOFLEX ■9-88.

e-AIRFLEX■400 vinegar vinyl/ethylene copolymer and 0.2 part of a Dioctyl sodium sulfosuccinate (American C) for wetting Lumi foil AEROSOL 0T-75) made by yanamid Company (aluminum (for foil wetting).

- Observed fiber tearing.

9-1 This example demonstrates the preparation of latex and its excellent adhesion during the early stages of the drying process. Demonstrates the ability to construct sexuality. The equipment and procedure described in Example 1 were used. First, step A in Table 1 Deionized water, ELVANOL■52-22, ELVANOL■5 in the amounts listed in 1-05, TERGITOL @NP-15, DOWFAX■2A1. Sodium acetate Lium, NALCO 2343, potassium persulfate, triallyl cyanurate, acetic acid Vinyl, vinyl chloride, butyl acrylate, and acrylic acid were charged into a kettle. Toad When heated to 67°C, vinyl acetate and vinyl chloride were added in the amounts listed in Step B in Table I. , butyl acrylate, acrylic acid, triallyl cyanurate and NALCO■23 43 was added to the reaction kettle over a period of 4 hours. Amount of potassium persulfate supplied and reaction procedure was the same as described in Example 1. The latex produced is 55.0% solids by weight. minutes and a viscosity of 4140 cps (Brookfield type LVT, No. 4 spin temperature, 60 rpm, 25°C).

For laminating plasticized PvC film to plywood, medium density board and Boblin cotton fabric. General test described in Example 3 using the above latex and examining peel adhesion The methods and conditions were used. The results recorded with bond/wire 1n (pli) are shown in Table ■ .

Freeze-thaw stability is an important property for aqueous polymer dispersions. La lacks freeze-thaw stability There are no examples of latex that solidifies when frozen and remains solid even after thawing. Seeds were frozen for 16 hours at -10°C and thawed for 8 hours at room temperature. The stability of latex was investigated under cold conditions. VAE latex solidifies in one cycle did.

The latex of this example passed through 5 cycles without any problems.

The results in Table 2 show that the aqueous polymer dispersion of the present invention has a low The results show that surprisingly good adhesion was achieved with respect to energy and hard-to-adhere surfaces. This unusually strong initial adhesion by the aqueous polymer dispersion of the present invention The dimensional stability of the laminate produced with the adhesive of the invention can be maintained shortly after lamination. , or (suggests that the handling of the laminate can be facilitated and its manufacture can be accelerated) do. Additionally, the results generally indicate that the adhesion increases with the passage of aging time and in this example 0, which shows an improvement as the amount of plasticizer post-added to the latex increases. The freeze-thaw stability of this latex was excellent.

Nine-two This example shows a latte with two types of poly(vinyl alcohol) used at different levels. The adhesion of this latex to a transparent float glass, showing the preparation of a x dispersion. Using the equipment described in Example I, a comparison was made with a commercial vinyl acetate/ethylene copolymer. Using the procedure and relative amounts of ingredients described in Example 3, ELVANOL 52-22 ．． Regarding the amount of ELVANOL ■51-05 and deionized water, see Step A in Table ■. This is shown below.

The resulting latex had a solids content of 52.6% by weight and a viscosity of 1360 cps (Blue field type LVT, N004 spindle, 60 rpm, 22°C) Ta.

The latex was coated onto Boblin cotton fabric with a #20 wire wound applicator. the covering A clear float glass plate was immediately placed on the covering cloth. This laminate overnight 2 The laminate was dried at 2°C and then tested for 180 degree peel strength on fin strips. I checked with Instron. Instron 12 on 50 bond scale The crosshead speed was set at in/min. Recorded with bond/wire 1n (pli) The results were as follows: Cloth adhesion to Nigarasu AIREFLEX■400 0.63 ^rREFLEX ■400' 0.56 The result is that the latex of this example uses a plasticizer. Excellent adhesion to transparent float glass plates with or without It is shown that. The adhesion is much higher than that of commercial VAE latex. Ta.

9-1 This example shows a latte with a small amount of vinyl crotonate and N~methylolacrylamide. This figure shows the preparation of the couscous. Its performance as a laminating adhesive was evaluated using commercially available vinyl acetate-ethylene. The device described in Example 1 compared with AIRFLEX 400 Using the procedure and relative amounts of ingredients described in Example 3, vinyl crotonate was Charged as shown in Table I, Step A and added as shown in Table I, Step B. Also, N - Methylol acrylamide was added as described in step B during surface finishing.

The resulting latex had a solids content of 54.0% by weight and a viscosity of 4655 cps (Brook Field type LVT, No. 4 spindle, 60 rpm, 25°C). Lamination of plasticized PvC film to medium density board and boblin cotton fabric using TEX The general test method and conditions described in Example 3, in which peel adhesion was investigated, were used.

The results recorded in bond/1 ain (pli) are shown in Table H.

The results show that this latex adheres plasticized PvC to medium density board and Boblin cotton fabric. This indicates that the laminating adhesive had excellent adhesion. The adhesion is There was also a significant improvement after thermal aging. Initial adhesion and adhesion after aging Both were higher than commercial vinyl acetate-ethylene adhesive emulsions.

r ■: Bo I P vinyl film 1 4” 2.04 1.32 2.8 6 (Masonai day 2 1 3.03 5.37 2.0 14’ 5.70 3.63 1.053b1 6.39 to 3.51” 4.8 4 to 3.74' 3.93 to l, 67"3,94"'4.65"°1.7 B"'14ζ 5.34 vs. 4.02" 4.83 vs. 5.89' 4.17 vs. 2 ．． 77″5, 78″° 4.93wI″ 4.08″’14’ 5.38 to 6 ．． 34" 4.46 to 4.37" 4, 48" 1" 4.42" 4 1 5.29 vs. 2.37” 4.96 vs. 3.74’ 2.42 vs. 1.71” 3 4.74 vs. 3.52" 3.36 vs. 4.21" 2.92 vs. 2.88"7 6.50 vs. 3.52 @ 5.18 vs. 3.88 @ 3.45 vs. 3.82'4' 1 6 ．． 69 vs. 3.33” 3.66 vs. 3.72’ 4.41 vs. 2.34’3 5.8 9 vs 4.02" 4.68 vs 4.35" 3.87 vs 2.97" 7 7.58 vs 3.03" 5.12 vs. 3.36" 3.95 vs. 2.17" 4" 1 6.67 vs. 4.52" 5.76 vs. 4.02" 4.67 vs. 1.85" 3 6.58 vs. 4 ．． 04″ 5.51 vs. 3.77” 5.29 vs. 3.45”7 5.51 vs. 4.3 2” 4.36 vs. 3.52” 8.32 vs. 9.14” 6@1 5.72 vs. 4.7 9" 2.93 vs. 2.74" 14" 9.95 vs. 5.55" 6.76 vs. 6.4 1' Umbrella - Ethi containing AERO3OL 0T-75 for pvc film wetting Comparison with Ren/vinyl acetate copolymer (AIRFLEX ■400).

a Aging at -60°C.

Contains b-5 parts of BENZOFLEX 9-88 plasticizer.

Part b'-5 (7) BENZOFt, EX■9-88 Eliminate plasticizer.

c Aging at -50°C.

d-2, 5 parts (7) BENZOFLEX ■9-88 Contains plasticizer gold.

e-3.5 parts (7) Contains BENZOFLEX ■9-88 plasticizer.

abstract poly(vinyl alcohol) and species consisting of poly[vinyl chloride and/or vinyl The adhesive, which is an aqueous dispersion of redene copolymer, is made of plasticized poly(vinyl chloride). Improved adhesion is provided for laminates containing low energy surfaces such as.

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Claims (10)

[Claims] 1. An adhesive set is applied to the surface of one or more layers and/or the support material to be laminated together. A method of manufacturing a laminate comprising applying a composition and then laminating the materials together. , water, poly(vinyl alcohol), and (a) vinyl chloride or vinyl chloride. Approximately 5 to 70% by weight (b) about 30-95% by weight of one or more ethylenically unsaturated carboxylates; and (c) repeating units composed of no more than about 5% by weight of other ethylenically unsaturated monomers; An adhesive composition comprising an aqueous dispersion containing an effective adhesive amount of a polymer essentially A method characterized by using. 2. The polymer (a) Vinyl chloride about 25-28% by weight, (b) Butyl acrylate about 37-43% by weight (c) about 29-35% by weight of vinyl acetate, (d) about 0.5% by weight of acrylic acid , (e) about 0.1% by weight of triallyl cyanurate; and (f) optionally N-methylate. Roll acrylamide approx. 0.5% by weight The method of claim 1, wherein the method is made from: 3. The polymer (a) Vinyl chloride about 25-28% by weight, (b) Butyl acrylate about 37-43% by weight (c) about 29-35% by weight of vinyl acetate, (d) about 0.5% by weight of acrylic acid , (e) about 0.1% by weight of vinyl crotonate and (f) N-methylolacrylamide 2. The method of claim 1, wherein the method is made from about 0.5% by weight. 4. Water, poly(vinyl alcohol) and (a) vinyl chloride or vinyl chloride Approximately 5-70% by weight of Liden (b) about 30-95% by weight of one or more ethylenically unsaturated carboxylates; and (c) repeating units composed of no more than about 5% by weight of other ethylenically unsaturated monomers; An adhesive composition comprising an aqueous dispersion containing an effective adhesive amount of a polymer essentially A laminate comprising a support attached to one or more layers using. 5. The polymer (a) Vinyl chloride about 25-28% by weight, (b) Butyl acrylate about 37-43% by weight (c) about 29-35% by weight of vinyl acetate, (d) about 0.5% by weight of acrylic acid , (e) about 0.1% by weight of triallyl cyanurate; and (f) optionally N-methylate. Roll acrylamide approx. 0.5% by weight 5. The laminate of claim 4 made of. 6. The polymer (a) Vinyl chloride about 25-28% by weight, (b) Butyl acrylate about 37-43% by weight (c) about 29-35% by weight of vinyl acetate, (d) about 0.5% by weight of acrylic acid , (e) about 0.1% by weight of vinyl crotonate and (f) N-methylolacrylamide 5. The laminate of claim 4, wherein the laminate is made of about 0.5% by weight. 7. Water, poly(vinyl alcohol) and (a) vinyl chloride or vinyl chloride Approximately 5-70% by weight of Liden (b) about 30-95% by weight of one or more ethylenically unsaturated carboxylates; and (c) repeating units composed of no more than about 5% by weight of other ethylenically unsaturated monomers; An adhesive composition that is an aqueous dispersion comprising an effective adhesive amount essentially of a polymer. 8. The polymer (a) Vinyl chloride about 25-28% by weight, (b) Butyl acrylate about 37-43% by weight (c) about 29-35% by weight of vinyl acetate, (d) about 0.5% by weight of acrylic acid , (e) about 0.1% by weight triallyl crotonate; and (f) optionally N-methyl Roll acrylamide approx. 0.5% by weight 8. The composition of claim 7 made from. 9. The polymer (a) Vinyl chloride about 25-28% by weight, (b) Butyl acrylate about 37-43% by weight (c) about 29-35% by weight of vinyl acetate, (d) about 0.5% by weight of acrylic acid , (e) about 0.1% by weight of vinyl crotonate and (f) N-methylolacrylamide 8. The composition of claim 7, wherein the composition is made up of about 0.5% by weight. 10. One or more laminating materials are poly(vinyl chloride), glass or metal foil. The method of claim 1 and claim 4, wherein the low energy, non-stick material is selected. laminate.