TW575647B - Process for producing emulsion pressure sensitive adhesive agent composition - Google Patents

Abstract

An emulsion type adhesive composition is obtained by polymerizing an ethylenically unsaturated monomer (E) having alkyl (meth)acrylate (e1) as main component, in presence of a resin emulsion (II) obtained by polymerizing an emulsification liquid (I). The emulsification liquid (I) is obtained by emulsifying a fat-soluble component containing ethylenically unsaturated monomer (A) and tackifier (B). An emulsion type adhesive composition is obtained by polymerizing an ethylenically unsaturated monomer (E) having alkyl (meth)acrylate (e1) as main component, in presence of a resin emulsion (II). The resin emulsion (II) is obtained by polymerizing an emulsification liquid (I) in the presence of a polymerization initiator (D). The emulsification liquid (I) is obtained by emulsifying a fat-soluble component containing ethylenically unsaturated monomer (A) having alkyl (meth)acrylate (a1) as main component, and tackifier (B) using an emulsifier (C) in an aqueous medium. The average particle diameter of the fat soluble component is 1 mum or less.

Description

^ / 5647 V. Description of the invention (l) Dengming belongs to the genus Kubentu, which is a kind of milk micro-needling needle ^ Specifically, regarding adhesiveness (special ^^ ^^ agent composition manufacturing method, more powerful, Adhesiveness to pure viscous Λ'polyolefins> and its ability to maintain whiteness) are all excellent in the previous method of manufacturing the composition of the adhesive agent. Adhesiveness (thin or: v: two-item gift gum 'By changing its composition, it can change its adhesion " Taguchi, cohesion balance', so it can be used as an adhesive or adhesive. Also, flat bucket + main, , W ding ^ into the mallet, and $ π In this case, in order to improve the adhesion (or adhesion =), it is generally necessary to add a resin that imparts adhesion. I The resin that imparts adhesion is not water-soluble, Therefore, the method of adding =, > solution to the solvent, or the method of adding as a water latex is adopted. However, in the former method, there is no advantage two as a water system and in the latter method, Adhesive resin-imparting particles and acrylic resin particles cannot be mixed uniformly, the adhesiveness of the obtained adhesive or adhesive sword is low, and the water resistance is also low, which causes many problems. In order to solve such problems, The following suggestions have been made. JP-A-Sho 5 4-2 3 6 4 1 will include a copolymerizable monomer containing an acrylic monomer, a crosslinkable functional group, and a polymer that can be dissolved in the former two in advance. High in at least one of the Emulsion polymerization of the molecular compound and the latex of the surfactant is carried out to obtain a water-moisture type adhesive composition. (2) JP 5-8-1 8 5 6 6 8 will be dissolved or separated in a mixture of crosslinkable monomer and (meth) acrylate

575647 V. Description of the invention (2) A complex obtained by dispersing an adhesive-imparting resin, or an emulsified composition obtained by dispersing the complex in water containing an emulsifier, while adding to the water-containing, emulsified In the polymerization solution of the agent and the polymerization catalyst, a copolymerized latex-type adhesive is obtained while performing polymerization. In addition to the above (1) and (2), the following suggestions have been made. (3) Japanese Patent Laid-Open No. 20 0 0-3 1 386 No. 5 contains 100 to 95% by weight of an alkyl (meth) acrylic acid alkyl group having 50 to 99.5 wt% of alkyl carbon atoms, 0 · 5 to 2 · 5 wt% of a mixed monomer of a monomer having a carboxyl group, a phenyl group, or an amino group, dissolving 0.5 to 5 parts by weight of a two, pre-adhesive resin and an oil-soluble polymerization initiator, It was emulsified and dispersed in an emulsified gas' solution to form monomers = water droplets with an average particle diameter of 1 V m or less, and then polymerized to obtain a latex-type adhesive. However, in the techniques disclosed in the above (1) and (2), there is no discussion on the dispersing or dispersion of the adhesive resin to form the emulsified dispersion of the mixed liquid. In use by usual :.聚合 In the case of polymerizing the emulsion obtained by emulsifying and dispersing, the more the amount of / advancing resin is used, the more stable the person chooses pre-adhesion M ^ Κ 〇 the more unstable, the obtained Φ chat stability Poor sex becomes a problem. In the technology disclosed in the above (1) to (3), the spoon meal is put, the adhesion of the hydrocarbon), the holding force, the adhesion with the substrate = raw, (: do n’t mean, do n’t ^ in ^ The performance of preventing whitening when it breaks) and other aspects have not been improved. Under the background of 7-person bonding, the object of the present invention is to provide excellent J / JOH / 5. Description of the invention (3) ^ Especially for the viscosity and water resistance of polyolefin (especially in water immersion) The present invention is a method for manufacturing an adhesive-type adhesive tackifier composition which is held up and held on the substrate. The properties of anti-whitening) are excellent in milk. The present inventors have solved the above problems with the present invention. That is to say, as of the date of issue: ;;: ㈣ 'completed the manufacturing method, which is characterized by: Zhiyue's glue-type adhesive composition will be composed of (meth) acrylic acid Adhesive agent (Β) ί =: ί ethyl ester insaturation ^ tt 1 | L,] (C) ,, | L;, B ^ ^ ^ ^ ^ homogeneous particles straight A] n official service of the above oil Soluble ingredients of Ping Lai are straightened to 1 · ο # m or less, so the polymerization initiator is removed in the name T-Yichengchenglihua [I], fat emulsion [Π]; and emulsion ⑴ Polymerize to obtain gum [Iη, polymerize with ethyl (meth) acrylic acid alkyl ether: two-component ethylenically unsaturated monomer (E) to obtain a latex type adhesive composition. In the present invention, From the viewpoints of adhesion to the substrate and water resistance (especially the ability to prevent blushing when immersed in water), the ethylenically unsaturated monomer (E) 'except for (fluorenyl) alkyl acrylate (el) In addition, it is preferable to include an unsaturated monomer (e2) containing a tertiary group, or an unsaturated monomer (e 2) containing a carboxyl group and an unsaturated monomer (e 3) containing a crosslinkable fluorene. ) (Except for the unsaturated monomer (e2) containing a carboxyl group.) In the present invention, the above-mentioned latex-type adhesive composition is preferably compounded with a cross-linking agent (F), so that the present invention can be significantly exerted. Effect.

C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 7 575647

V. Description of the invention (4) Embodiments of the invention A detailed description will be given below. The ethylenically unsaturated monomer (A) used in the present invention contains a (fluorenyl) acrylic acid group (U1) as a main component. Examples of such (fluorenyl) ^ dilute acid alkyl esters (a 1) include, for example, fluorenyl bis (fluorenyl) acrylate, ethyl (fluorenyl) acrylate, and n-propyl (fluorenyl) acrylate. , Isopropyl (fluorenyl) acrylate, n-butyl dragon (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (fluorenyl) acrylate, 2-ethylhexyl (meth) acrylate The number of carbon atoms such as ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (propyl) propionate, etc. is 1 ~ 8 alkyl (meth) acrylate alkyl, and (fluorenyl) nonyl acryl, isononyl (meth) acrylate, decyl (meth) propionate, and (fluorenyl) Isodecyl propionate, dodecyl (propenyl) propionate, (11) isopropyl ester of (meth) acrylic acid (Isofluorenyl) acrylic acid alkyl esters of (fluorenyl) isotridecyl acrylate and (fluorenyl) acrylic acid tetradecyl ester, etc. having alkyl groups having 9 or more carbon atoms. Of these & preferred alkyl (meth) acrylates having 1 to 8 carbon atoms, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl acrylate. The ethylenically unsaturated monomer (A) may contain a cross-linkable monomer (a 2) as a cross-linkable monomer in addition to the alkyl (meth) acrylate (a 1). a 2), for example, (1) a carboxyl group-containing monomer; (2) a hydroxyl group-containing monomer;

575647 V. Description of the invention (5) (3) monomer containing epoxy group; (4) monomer containing alkoxyphosphosilyl group; (5) containing at least one of acid amine group, methylol group or keto group Monofluorene (herein, the so-called "keto group" means a keto group or a keto-enol tautomeric hydrazone group); (6) a polyfunctional monomer. These cross-linkable monomers (A2) One or more types may be used in combination. Or 2 As the carboxyl group-containing monomer (1), acrylic acid, propylene dimer, methacrylic acid, crotonic acid, itaconic acid, and maleic acid may be mentioned; 1 as (2) Hydroxyl-containing monomers include (fluorenyl) acrylic acid-transylethyl, (fluorenyl) acrylic acid 2-hydroxypropyl, and the like; (3) as the monomer containing bad oxygen groups, Examples include (meth) acrylic acid glycerol vinegar, allyl glycidyl scale, and the like; and (100) examples include (4) alkoxy fluorinated silyl group-containing monomer (meth) propyloxyethyl Trimethoxysilane τ- (methyl) propoxyethyltriethoxysilane; τ- (meth) propyloxypropyltrimethoxysilane; Τ- (methyl ) Propoxypropyltriethoxy silicon sinter; r- (meth) acryloxypropylmethyldimethoxylithoxane r- (meth) acryloxypropyldimethylmethoxy Silane r_ (meth) propoxypropylmethyldiethoxylithium γ- (fluorenyl) propenyloxypropyldimethyl — — ^ ^ ^ ^ A ^ ^ T ethoxysilane -(Meth) acryloylpropyltritoxylate yaki-yaki-r- (meth) acryloxypropylmethyl-:-'T 丞 -Rolling Silane; C: \ 2D-C0DE \ 9M2 \ 91121999.ptd $ 9Page 575647 V. Description of the invention (6) r- (meth) acryloxypropyldifluorenylchlorosilane; 7 "-( fluorenyl) propoxypropyltripropoxylithium; r- (Meth) acryloxypropylfluorenyldipropoxysilane; r- (meth) acryloxypropyltributoxysilane; r- (fluorenyl) acryloxybutyltrimethoxysilane ; R_ (fluorenyl) propenyloxybenzyltrimethoxysilane; r- (fluorenyl) propenyloxyhexyltrimethoxysilane; r- (meth) propenyloxyhexyltriethoxysilane; r -(Meth) acryloxyoctyltrimethoxysilane; r-(fluorenyl) acryloxydecane Trimethoxysilane; (fluorenyl) propenyldodecyltrimethoxysilane; r- (fluorenyl) propenyloctadecyltrimethoxysilane; vinyltrimethoxysilane; Ethylenediethoxylate; vinyltripropoxysilane; vinylfluorenyldimethoxysilane; ethylene methyldiethoxylate; ethylenemethyldipropoxylate (5) As the monomer containing at least one of an amidino group, a hydroxyamidino group, or a keto group, there may be mentioned: acrylamide containing amidino group, amidinoacrylamide; N-hydroxymethyl acrylamide, butoxy-N-hydroxy acrylamide, a hydroxyamyl group; diacetone acrylamide containing a amine group and a keto group;

C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 10 575647 V. Description of the invention (7) Ketone-based (fluorenyl) acrylic acid 2- (ethyl acetoacetoxy) ethyl ester, acetamidine Allyl acetate; Examples of the polyfunctional monomer (6) include ethylene glycol di (fluorenyl) acrylate; diethylene glycol di (fluorenyl) acrylate; triethyl di (meth) acrylate Glycol esters; polyethylene glycol di (fluorenyl) acrylate; propylene glycol di (fluorenyl) acrylate; dipropylene glycol di (fluorenyl) acrylate; tripropylene glycol di (fluorenyl) acrylate; di (fluorenyl) Polypropylene glycol acrylate; Di (fluorenyl) acrylic acid-1,3-butanediol; Di (meth) acrylic acid-1,4-butanediol; Di (fluorenyl) acrylic acid_1 6-hexanedioxine; di (fluorenyl) acrylic acid-1,9-nonanediol ester; di (fluorenyl) neopentyl glycol acrylate; tris (fluorenyl) trihydroxyfluorenyl propane acrylate; Tetra (hydroxy) tetramethylfluorenyl acrylate tri (fluorenyl) acrylate; Tetra (hydroxy) tetramethylfluorenyl acrylate fluorenyl acrylate; glyceryl methacrylate acrylate; Phosphate; bis (Yue-yl) acrylate, diallyl phthalate; four-allyloxy-ethane; divinylbenzene;

C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 11 575647 V. Description of the invention (8) Tris (fluorenyl) allyl isocyanurate. Among the crosslinkable monomers (a 2), acrylic acid, fluorenyl acrylic acid, itaconic acid, 2-hydroxyethyl (fluorenyl) acrylate, glycidyl (fluorenyl) acrylate, and T-fluorene are particularly preferably used. Allyloxypropyltrimethylsilylsilane, r-methylpropyloxypropyldiethoxysilane, methylpropyloxypropylmethyldioxysilane, r-methylpropyloxy Propyl fluorenyl diethoxysilane, vinyl triethoxy silane, N-hydroxy fluorenyl propylene amine, diacetone propylene amine, 2- (ethyl acetone) ethyl acrylate, (Fluorenyl) propylene glycol acrylate, di (fluorenyl) dipropylene glycol acrylate, di (fluorenyl) tripropylene glycol acrylate, di (fluorenyl) ethylene glycol acrylate, di (fluorenyl) diethylene glycol acrylate , Triethylene glycol di (fluorenyl) acrylate, diallyl phthalate, divinylbenzene, and the like. In the present invention, the ethylenically unsaturated monomer (A), together with the (fluorenyl) alkyl acrylate (al), or with the (fluorenyl) alkyl acrylate (al) and a crosslinkable monomer It can also contain other copolymerizable monomers (a3) together. Examples of such other copolymerizable monomers (a3) include acrylic moon green, fluorenyl acrylonitrile, styrene, α-fluorenyl styrene, vinyl acetate, vinyl propionate, ethylene gas, and alkyl vinyl ether. , Dimethylaminoethyl (fluorenyl) acrylate, 2-methoxyethyl (fluorenyl) acrylate, Butoxyethyl (fluorenyl) acrylate, Trimethoxyethylene glycol (meth) acrylate Esters, etc. Among the above ethylenically unsaturated monomers (A), the ratio of the (fluorenyl) acrylic acid ester (a 1), the crosslinkable monomer (a 2), and other copolymerizable monomers (a 3) Preferably: (fluorenyl) alkyl acrylate (al) is 50 ~ 100wt%;

C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 12 575647 5. Description of the invention (9) Shameful monomer (a 2) is 0 ~ 2 0 W t%; copolymerizable monomer (a3) 0 ~ 50wt%. A better ratio is: (alkyl) alkyl acrylate (al) is 70 ~ 100% by weight; the monomer (a2) which can be used is 0 ~ 10% by weight; /, monomers copolymerizable with methadone (A3) is 0 to 30 wt%. Particularly preferred ratios are: alkyl) alkyl acrylate (31) is 80% to 100%; crosslinkable monomer a ", 0 to 5wt%; other copolymerizable monomers U3) is 0 ~ 20wt%.… When the content of alkyl methacrylate (a 1) is less than 5 Owt%, sufficient adhesion strength and adhesion cannot be provided, and the transparency of the coating film is low, = It is not advisable. When the content of the crosslinkable monomer (a2) exceeds 20%, the transparency of the coating film is low, and instability occurs during polymerization, which is also undesirable. § Copolymerizable monomer (a3) When the content exceeds 50% by weight, the adhesion is strong and the adhesion is low, and the transparency of the coating film is also low, which is not desirable. Also, if the adhesion-imparting agent ⑻ used in the present invention can be dissolved or dispersed in Ethylene unsaturated monomers (A) can be, for example: n Super Ester Λ-75 "(made by Arakawa Chemical Industry Co., Ltd.)," SuPer Ester Α-100 "(Arakawa Chemical Industry Co., Ltd. limited; 5er A —125 丨 丨 (Arakawa Chemical & Health Industry Co., Ltd. clothing) Temple pine balm, " Pensel D125 "(Arakawa Chemical (Industrial Co., Ltd.), nPensel D160 " (made by Arakawa Chemical Industry Co., Ltd.), " Rikatack PCJ "(manufactured by Physico-Finetec Industrial Co., Ltd.) polymerized rosin; w °) Temple` `Nikanol ΗΡ-1〇 〇 "(Mitsubishi Gas Chemical Industry Co., Ltd.

C: \ 2D-C0DE \ 9M2 \ 91121999.ptd Page 13 575647 V. Description of the invention (10) Made by Ling Gas Chemical Industry Co., Ltd.), nNanolol HP-iwr 丄 duv — Again ~ π Ίυ 子 _ ^ Schematic copy , Limited manufacturing), "Nikan〇l Η_8〇 " (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd. limited bow) and other xylene resins; Α Division YS Polyster τ-115n (Yasuhara Chemical Co., Ltd.), Mightyace G125 ' '(Yasuhara Chemical Co., Ltd.) and other terpene to phenol resins; FTR-6 120 "(Mitsui Petrochemical Industry Co., Ltd. " FTR-6100" (Mitsui Petrochemical Industry Co., Ltd. 1 stone resin; clothing) ) Temple Petroleum's other benzofuran 1 resins, terpene / vinyl acetate resins, etc. Bu Yi Yue Yue, Yi Xi Xi Bu 'are called styrene-styrene-butadiene-isoprene block i Polymers, resins, water objects, temples, arms, 7 π / ethylene-the present ethylene-isoprene intercalene, vinyl acetate copolymers, acrylic μ-shishi can be used. '骖Teramoto also saturated the vinyls mentioned above in Ben Maoming. Reagent (B) mixed, shaped, early fe (A) and adhesion-improving adhesion to 100 parts by weight of 1 part of ethylenically unsaturated monomer ⑴ 歹 phase by weight The best range is 10 ~ weigh ==: When the amount of kiss is less than 5wt%, not Atsushi $, 丨 Waseda imparts the adhesiveness of olefin (B) to olefin. Report ^ I sentence Adhesiveness, especially in the case of polymerization, because the polymerization becomes unavailable ..., U) Adhesiveness of 1 is more than 40wt ° / 〇, so it is not advisable and not enough to have sufficient adhesiveness And page 14 C: \ 2D-C0DE \ 9M2 \ 9ll21999.ptd 575647

Capacity: 5 T f unsaturated early body (A) and the oil that imparts the adhesive agent 赋予 [11 for emulsification with emulsifier (C) in the mass to prepare the ability to emulsify into a knife. Yes, there is no particular limitation. For example, a reactive (ionic or non-ionic) surfactant, a non-reactive (ionic or non-ionic) surfactant, or the like may be used alone or in combination. Among them, in consideration of water resistance, it is preferable to use a reactive surfactant. The reactive surfactant may be an ionic or nonionic surfactant having a radical reactivity with the ethylenically unsaturated monomer (A). Examples of the reactive surfactant include compounds having a structure represented by the following general formulas (η to (9). (Structural formula 1) .. ch2 to 0-ch2-CH = ch2

(3) R] 0 —c'H2-CH— o— (ch2— ch2— 〇) “x (structural formula 2) ^ ch = chr2 〇- (ch2-ch2-〇) -x (structural formula 3) CH2 — COORj x— ch— cooct2ch — ch2

C: \ 2D-C0DE \ 91-12 \ 91121999.ptd Page 15 575647 V. Description of the invention (12) Structural formula 4) COORi pv x— ch—COOCH2CH — Cl'h ~ 〇—ch2 CH ~ ai2 (4)

OH structural formula 5) (5) ch ^ L (ch2-ch2-0) „-x structural formula 6) \ ch2 = c-c- (r3) t〇

X P— (OH)] (6) Structural formula 7)

Oi2 = CH— CH2—O · (7) Structural formula 8) 01¾ — CH—CH2 — CH2

R plant 0 — CH2 — CH—〇iCH2 — CH2 — X (8) Structural formula 9) R —CH — CH2 — 0 — CH2 ~ CH = CH2

〇-(ch2— ch2— 〇) D-X iili Page 16 (9) C: \ 2D-CODE \ 91-12 \ 91121999.ptd 575647 V. Description of the invention (13) (In the above general formula (1) In (9), the core is an alkyl group, r2 is a hydrogen atom or a methyl group, R3 is an alkylene group, η is an integer of 1 or more, m and 1 are integers of 1 or more (m + l = 3), and X is Any of a hydrogen atom, s〇3NH4, and S03Na) As the commercial product, the nAdeka Reasoap SE-20N " (anionic), "Adeka Reas〇ap SE-10N" (anionic) "Adeka Reasoap ΝΕ-10π (non-ionic), Adeka Reasoap Ν-20-20 (non-ionic)," Adeka kasoap NE-30 "(non-ionic)," Adeka Reas〇ap NE — 4〇 "(non-ionic Type), " Adeka Reasoap SDX-73 0 "(anionic) ,,, Adeka

Reasoap SDX-731 "(anionic) ,, Adeka Reas〇ap ER-10" (non-ionic) ,, Adeka Reasoap ER-20n (non-ionic), Adeka Reasoap ER-30n (non-ionic) ' " Adeke

Reasoap £ R-40 "(non-ionic) ,, Adeka Reas〇ap sr-loir (anionic)," Adeka Reas〇ap SR—20N "(anionic) (the above is Asahi Chemical Industry Co., Ltd. Manufacturing); "Eleminol JS-2" (anionic), 'Elemin〇1 RS — 30π (anionic) (the above is manufactured by Sanyo Chemical Industry Co., Ltd.); " Latemul S-180A "(anionic ) ,,, Utemul s —18〇 ,, (anionic) (the above is manufactured by Kao Co., Ltd.); " Aqualon BC-05 " (anionic), "AqualON BC-1〇 |, (order ion Type), "AqUal〇n BC — 2〇" (anionic type), nAquai〇n ^ HS-05 " (anionic type), "Aqua] [〇n Hs-1〇π (anionic type), " Avalon HS -20 "(anionic)," AqualOn RN—10 "(non-ionic), Aqualon RN-20" (non-ionic), " AqualOn RN —3〇 " (non-

C: \ 2D-C0DE \ 91-12 \ 91121999.ptd p. 17 575647

(Ion type), " AQualon RN_5〇 " (non-ion type), " Fr0 ": 510 (anionic type), " Aqual〇n KH-〇5 " (anionic type), r 2 10 "KΓ ， ° " (anionic) (The above is the No.-Gongye Co., Ltd. | = Manufactured as MW TX ', (anionic) (Dongbang Chemical Industry Co., Ltd. The compounding amount of the above-mentioned etiquette (C), relative to 丨〇〇 The sum of the saturated monomer ⑴ and the adhesion-imparting agent ， is equal to the weight of the same degree. The range is one part by weight, particularly good = 1 weight = wound. When the emulsifier (c) is less than 0.5 part by weight At this time, the particle diameter of the oil-soluble ingredients is difficult to reach below # m, and the polymerization is not defined. = When the amount of the agent exceeds _ part, the polymerization is unstable, and although the coating film is reduced, it is not desirable. (C) In addition to being added to the emulsion [丨], it is also added to the polymerization parent in advance. &Quot; Next, the monomers containing (fluorenyl) alkyl acrylate (al) or potfish are described below. U2) and / or other copolymerizable monomers U3) ^ and an oil composed of a precursor (A) and an adhesion-imparting agent (B) Component ,,: medium with emulsifier (c) emulsified emulsion to obtain [n, so that the oil-soluble method 7 points average particle diameter of 1 · A m square or less. As a method for adding each component, it is preferable to dissolve the adhesion-imparting agent (B) in the ethylenically unsaturated monomer (a) in advance, and then add each component to it.的 The amount of water is relative to 00 parts by weight of ethylenically unsaturated monomer (A) and

Page 18 575647 Description of the invention (15) The person who imparts the adhesive agent (B) # ^, more preferably 80 to 300 parts by weight: special mouth ’and still more preferably 70 to 50 parts by weight. When the amount is less than 70 parts by weight: two, two: two two parts by weight. When the use of water is qualitatively reduced. When the water is over :: standing, the concentration of the stabilizer [I] during polymerization is too low by two to five. When Qiao =, because the concentration of the substance is too low, the composition of the latex-type adhesive obtained by Ling You is taken. When the cloth is low (during film formation), the dryness is reduced, so it is not possible to use an emulsifier in the composition, and emulsify the oil-soluble component composed of the </ 妾 · 妾 reagent (b) obtained from ethylene-based desaturation. The average particle diameter of the two T components is as follows, and the ratio of 1: 1 to 0.5 is particularly good. In the milk solution [I] ', when the average particle diameter of the oil-soluble component exceeds the meanwhile, the storage stability of the latex decreases and the water resistance decreases, and the effect of the present invention cannot be obtained. Less than 2: = The average particle diameter of the oil-soluble component reaches h 〇 _ below. Decoration and milk 1 :: fixed: the ingredients can be mixed and stirred randomly; temporarily also: 14 for emulsification treatment. However, for the purpose of the present invention, the special particle was made to have an average particle diameter of the oil / synthetic component exceeding 1.0. From m to a liquid [I,], this emulsion was then made into an oil-soluble average particle diameter. Emulsions less than u㈣. As far as the ritualized liquid [Γ] is concerned, it is preferable to pre-emulsify each component by mixing with a mixing device such as a homogeneous disperser or paddle searcher, and obtain the average particle diameter of the oil-soluble component. Above 1 · G // m, then this milk

575647

The chemical solution [1] was subjected to an emulsification treatment to obtain an oil, an emulsified solution π and 枓 below U㈣. The average particle size of 40% knife is used to disperse the emulsion [factory], and the average particle size is straight; i 彳 η is equal to the limit of oil-soluble components; the method of chemical liquidization does not have special treatment, ultrasonic treatment, and stirring Treatment, etc. = High pressure homogenizer method. Specially, from the viewpoint of processing with a high_ # ㈣1 置, the pressure of the emulsion with a narrower diameter than that of a household word, 倥, or knife blade is preferably! 〇 Ί '理. Cm2 when using a high-pressure homogenizer.锃 is 10 ~ 15_δ / α2, especially good 30 ~ 100 kg /, it does not cause the mixture to be inversely emulsified by the inverse emulsification device, preferably the temperature during the left emulsification 1 to 5 times, as long as it should be during the emulsification process It is usually suitable at about 5 ~ 60 ° C. The number of times the emulsion is supplied, that is, the number of passes. Right 0 After the above-mentioned emulsion [丨] is prepared, the emulsion [I] is polymerized by a polymerization initiator to prepare a resin emulsion [: [丨]. The following methods are listed: As a method (1), the entire emulsion [I] can be heated as it is and polymerized; a part of the emulsion [n] is heated to start polymerization, and then the remaining emulsion is added dropwise or in stages. A method for polymerizing liquid [I] (adding a polymerization initiator (D) dropwise as needed); and adding water to the reaction vessel (η 1) (a part of emulsifier (C) or a polymerization initiator may be added as required) (]))) A polymerization method in which the temperature is increased, and then all the bites are added dropwise and the emulsion [I] is added in stages. But there are no restrictions on this.

C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 20 575647 V. Description of the invention (17) The amount of the polymerization initiator (D) is relative to 100 parts by weight of the ethylenically unsaturated monomer (A), 05〜5 重量 份。 Preferably 0. 05 ~ 5 parts by weight. A more preferred range is 0.1 to 3 parts by weight. When the amount of the polymerization initiator is less than 0.05 parts by weight, the polymerization rate is too slow. On the other hand, when the amount of the polymerization initiator exceeds 5 parts by weight, the molecular weight of the resin is very low, the holding power is low, and it is not preferable. The polymerization initiator (D) is not particularly limited, and both water-soluble and oil-soluble ones can be used. Specific examples include alkyl peroxide, third butyl peroxide, cumene peroxide, P-xane hydroperoxide, lauryl peroxide, 3, 5, 5-trimethylhexanoyl peroxide, octyl peroxide, tert-butyl cumyl peroxide, phenyl peroxide, Dichlorophenylhydrazone peroxide, dicumyl peroxide, di-third butyl peroxide, 1,1-bis (third butyl peroxy) -3,3,5 -trifluorenyl ring Hexane, -3, 3, 5-trimethylcyclohexanone, diisobutyl peroxydicarbonate, di (2-ethyl) hexyl peroxydicarbonate, and tert-butyl peroxyisobutyrate Organic peroxides such as esters; azobisisobutyronitrile, azobisisobutyric acid dihydrazone, 2, 2-azobis (2,4-difluorenylvaleronitrile), 2,2-azobis (2-Amidinobutyronitrile); potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide; 4, 4'-azobis-4-cyano-valeric acid ammonium (amine) salt, 2, 2 '-Azobis (2-amidinoamidooxime) dihydrochloride, 2, 2' tetrahydrate -Azodibis (2-amidinobutyrylamine), dihydrochloride, 2,2'-Azobis (2-amidino-N- [1,1-bis (hydroxyamido) -2) -Hydroxyethyl] propanamide), 2, 2'-azobis [2-fluorenyl-N-O-hydroxyethyl)] propanamide; Examples of various redox catalysts (in this case) Down as

C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 21 575647 V. Description of the invention (18) Oxidant, using kiln-based peroxide, krypton oxygen: JII: potassium persulfate, hydrogen peroxide, The third hydrogen butoxide 1 is dioxin, propylbenzene peroxide, p-toluene powder, ascorbic acid, etc.). Sodium sulfate, sodium bisulfite, and white polymerization initiator (D) can be added before the start of the polymerization, or can be added to the polymer μ, or it can be added to the polymer before the emulsification and the polymer must be polymerized before polymerization. In the process of addition, or in the mixed solution of sexual reagents, the unsaturated monomer (A) is also added and the adhesion is being imparted. At the time of addition, it may be added after adding the emulsified liquid [I], or the hair conditioner (D) may be dissolved in another solvent and added. m… The polymerization initiator is made into an emulsified state.

Value buffer. In order to adjust the pH value of the pH value during polymerization in the above-mentioned polymerization method, in the above-mentioned polymerization method, / 7 + is used in the method described in (i), for example: Table 5 ± conditions & Special restrictions. But the temperature range is appropriate, at the beginning of the temperature rise: usually 4: 100 "right should be appropriate. Σ 仃 0.5 ~ 8 to 8 hours In the above method (ii), Jiang R ~ nc η t under After polymerization for 4 hours or 4 hours, the remaining emulsion ⑴ was added dropwise within about 40 ~ 90, ^ side / eight ^ side engraved. 1 ~ 5 hours solution Π], and then at the same temperature ^ 刀 刀 = 加The remaining emulsification is in the above reaction (-), and the aging reaction is added. Water is heated to 40 ~ 9 (TC, at 0 5 :, 'liquid, the amount of 5 to 300 wt%, v, tb ,, Γ τ Ί ^ ^ · Add or add ritualized liquid ⑴ to a knife batch or knife batch for about 5 hours, and then ripen at the same temperature. I Page 22 C: \ 2D-C0DE \ 9M2 \ 91121999.ptd 575647 V. Description of the invention (19) &quot; --- = the resin emulsion [Π] can be obtained as described above, at this time, the average particle diameter of the resin component in the resin emulsion [II] is 0.05 to 0.5, preferably 0. 1 to • 3 "m. The resin concentration of the resin latex [丨 丨] is preferably 10 to β, particularly preferably 20 to 55 wt%. In the present invention, 'in the presence of the above-mentioned resin latex [丨 I], (Methyl) 2ene Alkyl esters (e 1) as a main component of ethylenically unsaturated monomer (E) poly [theta]. Thus obtained emulsion type adhesive composition.

The above-mentioned ethylenically unsaturated monomer (E) contains alkyl (meth) acrylate as the main component (1) as the alkyl (meth) acrylate (el). The fluorenyl) alkyl acrylate U1) is the same. Among them, alkyl (meth) acrylates having 乂 zoalkyl 妷 atomic numbers of 丨 to 8 are particularly preferably used. (Meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (fluorenyl) n-butyl acrylate, 2-ethylhexyl acrylate. 3. This dilute unsaturated monomer (E), in addition to the above-mentioned (meth) acrylic acid alkyl, such as (el), preferably contains a carboxyl-containing unsaturated monomer (e2) and a crosslinkable group. Unsaturated monomer (e3) (but not including unsaturated monomer (e2) with carboxyl group). The unsaturated monomer (e 2) as the π carboxyl group can be mentioned in the foregoing description.

The ethylenically unsaturated monomer (A) described above has the same carboxyl group-containing monomer (丨) as the monomer (a2) having a crosslinkable property. As: The unsaturated monomer (e 3) which can be linked to a group (excluding the unsaturated # monomer (e 2) with a carboxyl group) 'can be mentioned as the ethylenically unsaturated monomer: (A) % Of hydroxyl-containing precursors (2), epoxy-containing monomers (3), and alkoxysilyl-containing monomers having crosslinkable properties

575647 V. Description of the invention (20) Monomer hydrazone, containing at least one of amido, methylol, and ketone groups (5) and polyfunctional monomer (6). Particularly preferably, a 2-group-containing monomer and a polyfunctional monomer (6) among the monomers (5) are used. It is most preferable to use the ketone group-containing monomer in the engraving (5) from the observation of the adhesiveness to the substrate and the performance of preventing blushing when immersed in water. Good results. It is also possible to use other copolymerizable monomers (e4). As such, the copolymerizable monomers (e4) include the same as those described in the above description of ethylenically unsaturated ^ early bodies (A). The copolymerizable monomer (a3) is the same monomer. Among the aforementioned ethylenically unsaturated monomers (E), the (fluorenyl) propylene ^ alkyl ester (el) contains a carboxyl group-containing unsaturated monomer (e2), and a s-saturated precursor (e3) containing a crosslinkable group. (Excluding the carboxyl group-containing unsaturated monomer (e2)) and the copolymerizable monomer (e4) thereof, preferably, the (meth) acrylic acid alkyl ester (el) is 50 to 99% by weight; Unsaturated monomer 10wt /. The unsaturated monomer (with) containing a parentable group is 0 ~; the other copolymerizable monomer (e4) is 0 ~ 49wt%. As a more preferred range, (alkyl methacrylate (el) is ~ 98.45wt%; saturating monomer (e2) containing carboxyl is 1.5 ~ 8wt%; unsaturated containing crosslinkable groups &quot; and The body (e3) is 0.05 ~ 3wt%; and the other copolymerizable monomer (64) is 0 ~ = .45Wt%. As a particularly preferred range, (meth) acrylic acid (EI) 80 ~ 97.9wt%; unsaturated monomer (e2) containing carboxyl group is 2 ~ 6 ^%; unsaturated monomer (e3) having crosslinkable group is 0.01 ~ 2wt%; and other 3 The copolymerized monomer (e4) is 0 to 17.9 wt%. ', When the ratio of (meth) acrylic acid (el) is less than 50%, it cannot be

_ C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 24 575647

Sufficient adhesive strength and adhesiveness are obtained. On the other hand, when it exceeds 99% by weight, the ‘retention force and adhesiveness with the substrate, and the ability to prevent whitening when immersed in water tend to decrease. When the ratio of the carboxyl group-containing monomer (e2) is 1% by weight, sufficient adhesion cannot be obtained, and the whitening prevention performance when the substrate is impregnated with adhesiveness, and when it exceeds ≧ 0% by weight, Anti-polymer 7 = Adhesion strength decreases, and it is unstable during polymerization. When the ratio of the unsaturated monomer (e3) of the cross-linking group is more than 5 wt%, the adhesion and adhesiveness are reduced, and the whitening prevention performance tends to decrease when the water is impregnated. 2 Other copolymerizable monomers (e4) When the proportion exceeds 4 9 wt%, the adhesion strength and the adhesiveness tend to decrease. Also * In the presence of the resin latex [Π] obtained above, there is no particular limitation on the polymerization of the above-mentioned ethylenic unsaturated monomer (E), and from the viewpoint of polymerization stability and properties, it is preferred that ( e 丨) ~ (e4) The ethylenically unsaturated monomer (E) is pre-emulsified in an aqueous medium, and the emulsion [丨] is polymerized in the resin latex [II]. When a pre-emulsified emulsion [液] is obtained, an emulsifier is preferably used. As the emulsifier, it is the same as that described in the emulsifier (c) described above, and one kind or two or more kinds can be used simultaneously. / When the emulsion [A] obtained by pre-emulsifying the ethylenically unsaturated monomer (E) is polymerized, the same polymerization initiator (D) as described above is used. The polymerization initiator (D) can be added to the polymerization flea in advance, or it can be added at the beginning of the polymerization. If necessary, a can be added during the polymerization, or it can be added to the ethylenically unsaturated monomer (E) before emulsification. ) May be added to the emulsified emulsion [曱]. When adding, you can put the aggregation

: \ 2D-C0DE \ 9M2 \ 9i 121999.ptd

575647 V. Description of the invention (22) Initiator (D) is added to other solvents; if the agent (D) is made into an emulsified state and then added, the dissolved polymerization initiation can be used as the method for adding the above components. itm ^ ^ ^ ^, and there are special restrictions, but it is better, the method using Tian Lihua (C) bath% in water and then add other ingredients, where = the emulsifier ⑹ is dissolved in ethyl unsaturated A method of adding other components to the mixed solution of the monomer (e) later. The compounding amount of the agent ， is preferably 100% by weight of ethylenic unsaturation = (E), and preferably 0.3 to 7 parts by weight. A more preferred range is 0.5 to 5 servings. When the blending amount of the emulsifier (C) is less than 0.3 parts by weight, sufficient etiquette performance cannot be maintained, and the polymerization stability is low. When the amount of the emulsifier (C) exceeds 7 parts by weight, the adhesion strength, the adhesion to the substrate, and the water resistance tend to decrease. The amount of water 'is preferably 25 to 200 parts by weight based on 1,000 parts by weight of the ethylenically unsaturated monomer (E). A more preferable range is 30 to 15 parts by weight. When the amount of water is less than 25 parts by weight, the viscosity of the emulsion [曱] is too high, and the stability of polymerization is reduced. On the other hand, when the amount of water used exceeds 200 parts by weight, the concentration of the obtained latex is too low, and the drying property during coating tends to decrease. Then, 'the temperature-elevation polymerization of the emulsion [曱] is started in the presence of the resin latex [II], and the amount of the polymerization initiator (D) at this time is relative to 100,000 parts by weight of the ethylenically unsaturated monomer (E). It is preferably 0. 3 to 5 parts by weight, and particularly preferably 0. 0 to 5 to 3 parts by weight. When the amount of the polymerization initiator (d) is lower than this range, the polymerization rate is slow. When the amount exceeds the range, the molecular weight of the resin is too low, and the strength of the resin tends to decrease. f During polymerization, the following methods can be cited, for example: resin emulsion

C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 26

575647 V. Description of the invention (23), [π] is mixed with emulsified liquid [曱] and then heated up in situ; in: fat; gum [say 11]-part of the emulsified liquid [甲], then starts to heat up A method for gathering the whole emulsion and adding the remaining emulsion [a] or batchwise or continuously into 仃; and adding the emulsion L 曱 in the presence of resin latex [π] or batchwise or continuously The method for performing polymerization is not limited to these methods. : The sub-polymerization temperature is not particularly limited, but is usually preferably 40 to 90. . Within the range of 0 f within the range of llj, add ammonia water, various water-soluble amines, sodium hydroxide = &gt; Valley fluid, potassium hydroxide aqueous solution and other test solutions, and adjust the pH value to 9 '. It is adjusted to 6-8, and the latex used as the latex type adhesive composition of this invention is obtained. In this case, the particle diameter of the latex is preferably 010 to 035, and particularly preferably 0.13 to 0.25 / zm. The content of the 'resin latex ⑴] in the latex obtained by Man II is 10 to 80% by weight, and more preferably 20 to 60% by weight, relative to the total solid content. '4 Sijia's range is 25 ~ 50wt%. When the content of the tree = latex [II] is less than 10 wt%, 'the sufficient adhesion strength to polystyrene cannot be guaranteed' @ When the content of the resin latex [Π] exceeds 8 (^ 〇 / 〇, due to the holding force It is not desirable to lower the ability to prevent whitening during water immersion, such as the agent (?) In the latex-type adhesive composition of the present invention thus obtained, and the effect of the present invention can be more significantly exerted. As this The cross-linking agent (F) used at the time is not particularly limited, and may be, for example, a carbodiimide compound ^ a sialine compound, ethylene oxide

C: \ 2D-CODE \ 9l-12 \ 91121999.ptd page 27 575647 5. Description of the invention (24) Compounds, hydrazine compounds, isocyanate compounds, melamine compounds, epoxy compounds, metal salts and metal salts, etc. . Among them, at least one compound selected from the group consisting of carbodiimide-based compounds, carbene-based compounds, ethyleneimine-based compounds, and hydrazine-based compounds is preferred, and carbodiimide-based compounds and hydrazine-based compounds are particularly preferred. As the carbodiimide-based compound, any compound containing at least two carbodiimide groups is sufficient, and as a commercial product, n C a r b 0 d i 1 i t eπ (manufactured by Nisshin Textile Co., Ltd.) is mentioned. As the β-oxazoline compound, any compound containing at least two ^ oxazoline groups may be used, and as a commercial product, π E ρ 〇 cr 〇 sπ (manufactured by Nippon Catalyst Co., Ltd.). As the ethyleneimine-based compound, a compound containing at least two or more ethyleneimine groups is sufficient, and as a commercial product, n Ch emit iten (manufactured by Nippon Catalyst Co., Ltd.) is mentioned. As the hydrazine compound, a compound containing at least two hydrazine groups is sufficient, and examples thereof include dihydrazine oxalate, dihydrazine malate, dihydrazine succinate, dihydrazine glutarate, dihydrazine adipic acid, and sebacic acid. Dihydrazine, dihydrazine maleate, dihydrazine fumarate, dihydrazine itaconic acid, etc. Examples of the isocyanate-based compound include fluorene diisocyanate, 4, 4'-diphenyl fluorene diisocyanate, hexamethylene diisocyanate, dimethyl diisocyanate, m-diphenyl diisocyanate, 1,5 -Isocyanate compounds such as naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated methanediisocyanate, hydrogenated dimethylenebenzene diisocyanate, isophorone diisocyanate, tetramethylene dimethylenebenzene diisocyanate; such as n S umidur

C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 28 575647 V. Description of the invention (25) Condensed polyisocyanate compounds of π (manufactured by Sumitomo Bayer Urethane), such as n Desmodur IL, HLn (Bayer A · G (Manufactured by the company), n Coronate ΕΗΠ (manufactured by Japan Polyurethane Industry Co., Ltd.), a polyisocyanate compound having an isocyanurate ring, such as "Sumidur L" (Sumitomo

The addition polyisocyanate compound (manufactured by Bayer Urethane Co., Ltd.), such as n Coronate HLn (manufactured by Japan Polyurethane Industry Co., Ltd.), may be used without any problem.

Examples of the melamine-based compound include (hexamethyloxy) melamine melamine and methyloxymethyl urea. As the epoxy-based compound, for example, "Denacor (manufactured by Nagase Kasei Kogyo Co., Ltd.)," "Danacast" (manufactured by Nagase Kasei Kogyo Co., Ltd.), etc. As the metal salt and the metal salt, there may be Examples of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, molybdenum, magnesium, vanadium, chromium, zirconium, etc. are ethylene chelate salts of acetic acid (EDTA), and ammonium acetate-ammonium salts.杳 Salt salt temple of carbonate-ammonium.

The compounding amount of the cross-linking agent (F) varies depending on the type thereof. The solid content in the phasor parts of the latex is usually 0.05 to 10, 0.8 to 5 parts by weight, and particularly preferably 〇i. When the weight of the vehicle is less than 0.05 parts by weight, when the weight of the car is less than 0.05 parts by weight, when the weight of f is insufficient, the adhesive strength and adhesiveness tend to be lower than 5 miles. In the present invention, according to the requirements, The latex obtained above can be appropriately added

Page 575647

Coating performance improvers, thickeners, anti-corrosion and anti-mildew additives, melt stabilizers, plasticizers, high boiling point solvents, additives before and during polymerization can be added. ", Anti-recording agent, Kang Jie solvent and fillers, etc., in the polymerization of the latex-type adhesive composition of the present invention, the polymerization almost produces agglomerates during polymerization, its excellent storage stability #, adhesion (especially for The adhesion of the fine hydrocarbons), the holding power, the adhesion to the substrate, and the water resistance (the ability to prevent whitening when immersed in water) are all excellent. Examples The present invention will be specifically described by way of examples below. When it comes to &quot;% &quot;, &quot; parts, except for the transmittance (%), all are based on weight. Example 1 "Preparation of Resin Latex [II] (First Step Polymerization)" Will contain 55.8 parts of 2-ethylhexyl acrylate (ai), 30 parts of n-butyl acrylate (al), 10 parts of methyl methyl acrylate, 4 parts of acrylic acid (a2), 0.2 parts of tripropylene glycol diacrylate (a2) And 5 (^ "&quot; Super Ester A- 1 2 5π (B) (rosin ester-adhesive agent: made by Arakawa Chemical Industry Co., Ltd.) was added to a solution dissolved in 90 parts of water. 1 · 〇Part disodium hydrogen dodecanoate, 4.5 parts emulsifier (C) (Asahi Chemical Industry Co., Ltd. In an aqueous solution of "SE-100Nπ" manufactured by Toka Co., Ltd., it was mixed with a homogenizer and pre-emulsified. The average particle size of the oil-soluble components of the obtained emulsion [I,] was 5 // m. The average particle diameter was calculated from the scattering intensity distribution using a dynamic light scattering photometer DLS-70 0 (manufactured by Otsuka Electronics Co., Ltd.) (the same applies hereinafter). Then, a high-pressure homogenizer (manufactured by Gaul in Co., Ltd.) was used. of

C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 30 575647 V. Description of Invention (27)

Homogenizer) This emulsion [Γ] was treated once under a pressure of 50 kg / cv, and then treated three times under a pressure of 300 kg / cm2 to obtain 34 5.5 parts of oil-soluble component average particles. Emulsion [I] with a diameter of 0 · 5. In addition, an initiator solution was prepared by dissolving 1.0 part of ammonium persulfate as a polymerization initiator in 1 g of water. Then 'into a polymerization kettle, add 50 parts of water and 172.8 parts of the above-mentioned emulsion [I], warm up to an internal temperature of 80 ° C, add 25% (5 parts) of the above initiator solution, at 80 ° C Polymerization was carried out for 30 minutes, and then the remaining emulsion [I] and 25% (5 parts) of the initiator solution were added dropwise within 30 minutes at 8 ° C for polymerization. Thereafter, it was performed at 80 ° C for another hour. Polymerization to obtain resin latex [II] (average particle diameter 0.1 / zm, resin concentration 43. 9%). This resin concentration is determined by the residue content after drying this resin latex for 3 hours at 110 ° C. Calculated (the same below). <Preparation of the latex-type adhesive composition (second step polymerization)> Then, 1 3 0 · 2 parts of 2-ethylhexyl acrylate (e 1), 7 0. A mixture of 0 parts of n-butyl acrylate (el), 23.3 parts of methyl methacrylate (ei), 9.3 parts of acrylic acid (e2), and 0.47 parts of tripropylene glycol diacrylate (e3) was added to the In 110 parts of water, 1.6 parts of an emulsifier (C) (SE-10N manufactured by Asahi Chemical Industry Co., Ltd.) was dissolved in an aqueous solution, and the mixture was stirred and mixed with a homogenizer. It was pre-emulsified to obtain 344 · 9 parts of emulsified liquid [P]. Then, this emulsified liquid [P] was dropped with 3 3% (6.6 parts) of the initiator solution at 80 ° C for 3 hours. Add to the resin latex [II] obtained above, after the dropwise addition, add the remaining 17% (3.4 parts) in the initiator solution,

C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 31 5 575647 V. Description of the invention (28) Polymerization was then performed at 80 t for another 2 hours.

After the polymerization is completed, the non-volatile content of the latex obtained by adjusting the pH value with 5% ammonia water is 49%, and the viscosity is 1 500 mPa · P 〇 1 7 // m. The viscosity is at 25 ° C. Use the "B-type viscosity outside", after direct observation (the same below). (Measurement of the amount of coarse particles) at X ° Pass 100 g of the obtained latex (Em) through a 200-mesh sieve, and dry the filter components (agglomerates: coarse particles) for 3 hours, and measure the amount of the coarse particles ^ (Mg / Eml00g). , Y, &lt; Latex-type adhesive composition compounded with a cross-linking agent (F)> Added to 100 parts of the obtained latex and mixed them. ▼, V—, 〇4 '' manufactured by Co., Ltd., 〇5. 5 parts are 4 coating properties &amp; good fluorine-containing dipping and wetting agents (improving secondary wetting performance) (manufactured by Neos Co., Ltd.) ， 丨 「〇〇 &quot;) and the thickening agent (&quot; UH — 54 manufactured by Asahi Denka Kagaku Kogyo Co., Ltd.) The viscosity was adjusted to 10,000 mPa · s to obtain milk as a target, Can. The obtained latex-type anchoring agent composition was evaluated as follows. (Storage stability) The thus-obtained latex-type adhesive agent was allowed to stand at 40 t for 6 months, and then observed whether there was an increase in viscosity or Shen Dianwu. Or the separation was evaluated by the following criteria: ○ No increase in viscosity, sediment or separation ·, X: Increase in viscosity, sediment or separation.,

Page 32 575647 Description of the fifth invention (29) The obtained latex-type adhesive composition is coated on a release paper so that the thickness after drying is 2 0 // m, and it is dried at 100 t for 5 minutes. 'Laminate it on a 50 &amp; PET (polyester) film substrate or a vacuum seal (the substrate is a PET film) on the aluminum surface of the substrate to obtain a bonded thin film.' Evaluation of physical properties. (Adhesive strength) In the above adhesive film (product using PET film as the base material), after peeling the release paper, it is tested with stainless steel plate (SUS3 04) and polyethylene (PE) plate (Japanese Test Plate standard test) (Board) Adhered at 20 ° C and 65% relative humidity, and measured in accordance with JISZ 0 2 37 7 adhesive strength measurement method. Peeling strength (gf / 25_). (Retention force) In the above adhesive film (product using a PET substrate), after peeling the release paper, the test piece was adhered to a test plate of a stainless steel plate (SUS3 04) with an adhesive area of 25 mm x 2 5 mm, and the temperature was 80 ° C. Under the condition of 50% relative humidity and a load of 1 kg, the sliding force (mm) of the adhesive film and the thickness of the adhesive film after 24 hours were measured according to the holding force measurement method of j I s Z 0 2 3 7 Of course, the time (minutes) for which the adhesive film falls, without slipping (slip: 0_), the adhesive film will not fall. (Visco ball test) Using a J. dow type ball test machine, under the condition of 20 t and 65% relative humidity, the test piece at 25 mm X 100 mm was measured at an angle of 30 °. The number of the ball with the largest diameter that stops on the I interface. (Adhesion to substrate)

575647 V. Description of the invention (30) In the above adhesive film (using the substrate of vacuum aluminizing), the same test as the adhesion strength test of the stainless steel plate (SUS3 04) is performed, and the peel strength (g / 25mm) ) And peeling state were evaluated for adhesion to the substrate, and then comprehensively evaluated. The peeling state and the evaluation criteria of the comprehensive evaluation were performed as follows. [Peeling state] A: The surface of the adhered body is peeled (peeled off the interface with the adherend) or the cohesive layer is broken (broken in the middle of the adhesive layer). B: The substrate is peeled off ( Delamination on the interface with the substrate) · [Comprehensive evaluation] '〇. Peeling is sorrowful by A of the adherend; 丨 the surface is peeled or the cohesive layer is broken, and the peeling strength is 100 g / 2 5 mm or more; △ • Peeling state is separated from the substrate interface / ΟΓ, magazine; 丨 ® when the brake is off, peeling strength is 1 00 0g / 2 5mm or more; &amp; X: peeling state When it is peeled on the substrate interface κ 4 丨 1 age: ^. Ho; when the peel strength is less than 1000/2 5mm. (Protection against whitening when immersed in water) The above-mentioned adhesive film (made of PET film &amp; width: 2 release mold paper) was adhered to a glass plate, and was duplexed at 〇〇Γ and UC. Immerse in warm water for 3 days, then take it out of the water, and immediately measure the transmittance (%). This is performed in accordance with the ° 'system of Japan Electric Color Industry Co., Ltd., as a blank sample during measurement, 2ZV; 80 / The test strip for measuring the color of the user (that is, the sample of the knee of Example 2 * kneaded with two pieces of water stuck on a glass plate).

C: \ 2D-C0DE \ 91-12 \ 91121999.ptd Page 34 575647 V. Description of the invention (31) <Preparation of resin latex [II] (the first polymerization step)> will contain 30 · 9 parts of acrylic acid-2 -Ethylhexyl (al), 60 parts of n-butyl acrylate (al), 5 parts of methacrylic acid vinegar (al), 4 parts of acrylic acid (a2), 0.1 part of tripropylene glycol diacrylate Ester (a2) and 50 parts of &quot; Super Ester A- 1 2 5π (B) (rosin ester-adhesive agent: made by Arakawa Chemical Industry Co., Ltd.) was added to dissolve in 1 90 parts of water 1 0 parts of disodium hydrogen phosphate dodecahydrate and 4 5 parts of an emulsifier (C) (SE-1 0N manufactured by Asahi Chemical Industry Co., Ltd.) were pre-emulsified by stirring and mixing with a homogenizer. The average particle diameter of the oil-soluble components of the obtained emulsion [I,] was 5 // m. Then, this emulsion [I '] was treated once with a high-pressure homogenizer ("G Homogen izern" manufactured by Gau 1 i η) under a pressure of 50 kg / cm2, and a pressure of 300 kg / cm2 The treatment was performed 3 times to obtain 3 45 · 5 parts of an emulsion [I], and the average particle diameter of the oil-soluble component thereof was 0.1 5 / zm. In addition, "1.0 part of ammonium persulfate as a polymerization initiator was dissolved in 19.0 parts of water" to prepare an initiator solution. Then 'add 50 parts of water, 172 · 8 parts of the above-mentioned emulsion [I] to the polymerization dad, warm up to an internal temperature of 80 ° C, and add 25% (5 parts) of the above initiator solution at 80 ° C. After polymerization for 30 minutes at ° C, the remaining emulsion [I] and 25% (5 parts) of the initiator solution were added dropwise at 80 ° C and 30 minutes for polymerization. Thereafter, polymerization was further performed at 80 ° C for 1 hour to obtain a resin latex [π] (average particle diameter of 0.14 / zm, resin concentration of 43.9%). <Preparation of the latex-type adhesive composition of the present invention (second step polymerization)> Then, 72.1 parts of 2-ethylhexyl acrylate (el) and 140 parts of propylamidine

C: \ 2D-mDE \ 9M2 \ 91121999.ptd Page 35 575647 V. Description of the invention (32) n-butyl acid (e 1), 1 1 · 7 parts of fluorenyl acrylate (e 1), 9 · 3 A mixture of 3 parts of propylene (e 2) and 0. 2 parts of tripropylene glycol diacrylate (e 3) was added to 1 10 parts of water to dissolve 1.6 parts of emulsifier (C) (Asahi Denka Kogyo In the aqueous solution (n SE-1 Ο N) manufactured by Co., Ltd., pre-emulsification was performed by mixing with a homogenizer to obtain 344.9 parts of emulsion [P]. Then, at 80 C and within 3 hours, this emulsion [P] and 33% (6.6 parts) of the initiator solution were added dropwise to the resin latex [丨 j] obtained above ' After the dropwise addition was completed, 'the remaining 17% initiator solution (3.4 parts) was added, and then polymerization was performed at 80 ° C for another 2 hours. After the polymerization was completed, the pH was adjusted to 7.5 with 5% ammonia water. The nonvolatile content of the obtained latex was 49%, the viscosity was 18 0 0 m P a · s, and the particle diameter was 0 · 1 7 / / m. The obtained latex was evaluated in the same manner as in Example 1. To 100 parts of the obtained latex, 2 parts of a zozoline compound (E ρ 〇cr 〇s K-2 0 1 〇E, manufactured by Nippon Catalysts Co., Ltd.) as a crosslinking agent (F), 0 .05 parts of fluorine-containing wetting agent (n FT- 100 ″ manufactured by Neos Co., Ltd.) as a coating performance improver and an appropriate amount of thickener (n UH-5 4 Γ manufactured by Asahi Kasei Chemical Co., Ltd.) Mix and adjust the viscosity to 1000 OmPa · s. A target latex-type adhesive composition is obtained. The obtained latex-type adhesive composition is subjected to the same stability evaluation and adhesive property evaluation as the examples. Example 3 In Example 1, except that the cross-linking agent (F) was changed to 0.3 parts of 2,2-dimethylolbutanol-tr is (Nippon Catalysts Co., Ltd. Except for Chemitite PZ-33) manufactured by the company, it was carried out as it is to obtain latex

575647 V. Description of the invention (33) type adhesive composition. The obtained latex-type adhesive composition was subjected to the same standing stability evaluation and adhesive property evaluation as in Example 1. Example 4 In Example 1, except that the amount of 2-ethylhexyl acrylate (a 1) was changed to 55.0 parts in the first polymerization step, and 0.2 parts of tripropylene glycol diacrylate ( a2) was changed to 1.0 part of diacetone amine amine (a2), and in the second step poly-eight, the amount of 2-ethylhexyl acrylate (al) was changed to 28. 3 parts, 0.47 wound- Monopropionate dipropionate ^ Sf · S purpose (e 3) was changed to 2.3 parts dipropylene g with amine acrylate (e 3), all were carried out as is, the nonvolatile content of the obtained latex was 4 g% , Viscosity is 1660 mPa · s, and particle diameter is 0.17 // m. The obtained latex was subjected to the same evaluation as in Example 1. To 100 parts of the obtained latex, 0.3 part of dihydrazine adipate (manufactured by Dachaku Chemical Co., Ltd.) as a hydrazine compound of the crosslinking agent (F) was added, and 0.2 parts of the latex was used as a coating performance improver. Fluorine leaching agent (nFT-100n manufactured by Neos Co., Ltd.) and an appropriate amount of tackifier (made by Asahi Denka Kogyo Co., Ltd., 1 11Η-54Γ) are mixed to adjust the viscosity to 1000 mPa · s to obtain a latex-type adhesive.剂 组合 物。 Composition. The obtained latex-type adhesive composition was subjected to the same storage stability and adhesive property evaluation as in Example 1. Example 5 In Example 4, except that 1.0 part of acrylic acid-2 to acetamyloxyethyl acetate (a 2) was used instead of 1.0 part of diacetone propyl amine (a 2), all were carried out according to the example. 4 Proceed. Example 6 In Example 4, except that 1.0 part of ethyl allyl acetate (a2) was used instead

C: \ 2D-CODE \ 9M2 \ 91121999.ptd page 37 575647 V. Description of the invention (34) Except for 1.0 part of diacetone acrylamide (a2), Example 7 is followed by Example 4. In Example 1, p + bondability η is reduced: D ~ 1 2 5π (Polymerized rosin esters impart adhesion to the f-type agent Kangawa Chemical Co., Ltd., &quot; Super ESter A ] 25 ”(b) (made by ^ = + Co., Ltd.) instead of„ 1 Chemical Worker i. Adhesive Reagents for Adhesion: Made by Ara Corporation). The viscosity is BOOmPa. S, and the particle diameter is 疋 0.17. The obtained latex is subjected to the same evaluation as in Example}. The obtained latex is the same as in Example 丨 and a latex-type adhesive composition to be obtained is obtained. The composition of the agent was subjected to the same evaluation of storage stability and adhesive properties as in Example 1. Example 8 In Example 1, except that "YS — Polyster — N — 125” (terpene — stupid resins was used to provide adhesion) Reagent: γ asuhara C hemica 1 Co., Ltd.) instead of 'Super Ester A-125n (Rosin ester adhesion-promoting agent: Arakawa Chemical Industry Co., Ltd.), all were carried out as-is, the obtained latex Non-volatile content is 49%, viscosity is 1 40 0mpa · s, particle diameter is 0.17 // m. The obtained latex was subjected to the same evaluation as in Example 1. Using the obtained latex, the same latex as in Example 1 was used to obtain a latex-type adhesive composition, and the obtained latex-type The adhesive composition was subjected to the same storage stability and adhesive property evaluation as in Example 1. Example 9 In Example 1, except for the acrylic acid polymerized in the first step and the second polymerized step,

C: \ 2D-OODE \ 91-12 \ 91121999.ptd Page 38 575647

«Liyang wood fills the halve, and the reduced amount is increased except for the increase '. The nonvolatile content of the obtained latex is 4 9 〇4 occupancy 疋 8 0 〇mpa · s, the particle diameter is 0 · 1 6 // m. As a result, the same evaluation as in Example 1 was performed. The gift glue is used as the cross-linking agent (F) except for 1.5 parts of carbodiimide-based Heqing Textile Co., Ltd. "ν_〇4"). A latex-type adhesive composition was obtained, and the original d composition of Example 1 was subjected to the same placement stability and adhesion t evaluation as that of Example i. Evaluation of ijfejyj In Example 1, except for the first polymerization and the first polymerization, The Xia of the two-step polymerization was increased to 1.5 times, and the increased amount was reduced by reducing the acrylic acid— 2 to its equilibrium time, and all were carried out as it was. The non-volatile di-ester of the obtained latex was 47. 5%, and the viscosity was 2 0 0 mPa · s, a latex having a particle diameter of 0.18 X difluorene was subjected to the same evaluation as in Example 丨. 0.75 parts of carbodiimide was obtained, except that it was used as a crosslinking agent (F). Except for n V_ 0 4π) manufactured by Qingfang Textile Co., Ltd., all of them were processed in the same manner as described above to obtain a latex-type adhesive composition, and the obtained milk f = composition was subjected to the same storage stability and adhesion as in Example i. Physical properties and evaluation «Example 11 In Example 4, except for the first step polymerization and the first 1/3 less salty stage polymerization, the amount of reduction increases with dilute two - acid 2 'ethylhexyl outside said to make up, as it were carried out, to obtain latex nonvolatile

C: \ 2D-CODE \ 9M2 \ 9ll21999.ptd

575647 V. Description of the invention (36) The content is 49%, the viscosity is 12 00 mPa · s, and the particle diameter is 0.17 / zm. The obtained latex was subjected to the same evaluation as in Example 1. Except for using 0.5 part of dihydrazine adipate (manufactured by Otsuka Chemical Co., Ltd.) as the cross-linking agent (F), the procedure was carried out as in Example 1 to obtain a latex-type adhesive composition, and the obtained latex-type adhesive was used. The agent composition was subjected to the same storage stability and adhesion properties evaluation as in Example 1. Example 1 2 In Example 4, except that the amount of diacetone acrylamide in the first step polymerization and the second step polymerization was doubled, and the increased amount was balanced by reducing 2-ethylhexyl acrylate. , All are carried out as is, the non-volatile content of the obtained latex is 49%, the viscosity is 190 mPa · s, and the particle diameter is 0.17 // m. The obtained latex was subjected to the same evaluation as in Example 1. Except that 0.15 parts of dihydrazine adipate (manufactured by Otsuka Chemical Co., Ltd.) was used as the cross-linking agent (F), the procedure was carried out as in Example 1 to obtain a latex-type adhesive composition. The adhesive composition was subjected to the same storage stability and adhesive property evaluation as in Example 1. Comparison Example 1 In Comparative Example 1, the emulsion [I,] (疋 5 μm of the oil-soluble component) was not processed by a pressure homogenizer (nHomogenizeri manufactured by gau 1 i η). , As it is (Step _ 〒 to resin latex (the average particle diameter is 0.12 //: σ 'to get 43.9%). Using the obtained resin latex, Jin Fen said, Chen degree 疋 20_Pa · s, particle diameter Is 0.15 „, for the preparation of latex-type coating agents

575647 V. Description of the invention (37) Finished product 'The same evaluation as in Example 1 was performed on the obtained latex-type adhesive composition. Comparative Example 2 Will contain 55.8 parts of 2-ethylhexyl acrylate (al), 30 parts of n-butyl acrylate (a 1), 10 parts of methyl methacrylate (a!), 4 parts of acrylic acid (a 2) 0, 2 parts of tripropylene glycol diacrylate (a2) and 50 parts of a mixed solution of Super Ester A-1 2 5π (B) (adhesive agent for giving rosin esters · made by Arakawa Chemical Industry Co., Ltd.) It was added to a solution in which 1.0 part of dibasic hydrogen dibasic acid 11-hydrate and 4 · 5 parts of an emulsifier ("SE-10" manufactured by Asahi Chemical Industry Co., Ltd.) were dissolved in 190 parts of water. Stir and mix with a homogenizer for pre-emulsification. The average particle diameter of the oil-soluble component of the obtained emulsion [I '] was 5 ν m. Then, this latex was treated with a high-pressure homogenizer ("Homogenizer" manufactured by Gaul in) at a pressure of 50 kg / cm2 once, and 3 times at a pressure of 300 kg / cm2 to obtain 3 4 5 5 parts of emulsion [I], the average particle diameter of its oil-soluble component is 0.15 "m. In addition, 0.5 part of ammonium persulfate as a polymerization initiator was dissolved in 9, 5 parts of water to prepare an initiator solution. Then, 50 parts of water and 172.8 parts of the above-mentioned emulsion [1] liter / JDI were charged into a polymerization kettle. To the inside, Lida 80 c, add 50% (5 wounds) of the above initiator solution, polymerize at 80 C for 30 minutes, and add the remaining emulsion dropwise within 80 minutes and 30 minutes [I ] Polymerize with the remaining initiator solution (5 parts), and add an additional hour of polymerization at 80 ° C. After cooling, the ammonia was adjusted to pH 7.5, and the non-volatile content of the obtained Rusheng was complex, viscous

Page 575647

The particle diameter is 0.14 // m. V. Description of the invention (38) Degree 80mPa · s Comparative Example 3 In Comparative Example 2, except that &quot; Super Ester A ~ 125Π γ melamine esters are used to give adhesive agents: (Arakawa Chemical Industry Co., Ltd.) was changed to 15 parts, the amount of water was changed to 97 · 2 parts, the f of disodium hydrogen phosphate dodecahydrate was changed to 0.3 parts, and the emulsifier (C) (Asahi Denki Chemical Co., Ltd. nSE-10N manufactured by Co., Ltd. "is changed to 3.5 parts, all as is, and an emulsion having an average particle diameter of oil-soluble components of 0.2 vm is obtained. [I], and except that the amount of water in the polymerization kettle was changed to 〇〇, the same polymerization was carried out to obtain a non-volatile content of 48.5%, a viscosity of 15 mPa. S, a particle diameter of 0, 2 0 // m latex The same procedure was used as in Example 1 to obtain a latex-type adhesive composition. The obtained latex-type adhesive composition was evaluated in the same manner as in Example 1. Comparative Example j In Example 1, Except for omitting n Super Ester a-125π (B) (Rosin esters for adhesive properties: Arakawa Chemical Industries Co., Ltd.), except that the first step polymerization was performed as it is, and then the second step polymerization was performed to obtain 43% non-volatile matter, viscosity 100 mPa · s, and particle diameter 0 · η. The emulsified &quot; Super Ester A-125, 'was added to the latex in the same manner as in Example u /, and then the same cross-linking agent (F), and cloth performance improver and tackifier were added as in Example 1. A latex-type adhesive composition 1 was obtained. The obtained latex-type adhesive composition was subjected to the same <evaluation result summary> as in Example 1.

C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 42 575647 V. Description of the invention (39) Tables 1 to 3 show the evaluation results of Examples 1 to 12 and Comparative Examples 1 to 4. Table 1 Amount of coarse particles (mg / EmlOOg) Storage stability Example 1 0.1 1 〇 Example 2 0.1 〇 Example 3 0. 1 〇 Example 4 0. 2 〇 Example 5 0. 2 〇 Example 6 0. 2 〇 Example 7 0. 2 〇 Example 8 0. 2 〇 Example 9 0. 1 〇 Example 1 0 0. 3 〇 Example 11 0. 1 〇 Example 1 2 0. 3 〇 Comparison Example 1 1 0 0 or more X Comparative example 2 0.2 2 〇 Comparative example 3 0.2 2 〇 Comparative example 4 0.5 5 〇

C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 43 575647 V. Description of the invention (40) Table 2 -— lv / 1SS do§ Rl δ # ϋ a ^ os fis ^ K- sooos (Lonosbu ( 900 9x0 Bu sss (coco (900 s (900 s (Los (9 inch s (800

Aoooo Bu) sz Bu) 00〇〇 ooos 9) 00 Bu 000900 90? Sooo

ZOLOZ

CNJOS Bu) 00〇〇 3009

(06.30S 鐾 铛 ffsns (inch 9 &lt; 1) 00 002 (89.101) 009 2

(OL

Hos II s (91 (99 s

(OL

(OA s (91 s s

(OA iloooo

(IOSA 91) 00

Moooo

Hoog

Hos

AIOOOO molol

ZIOOOO

SOOCQ

Moooo H) os (inch Bu.SOOCO II -ss ss

Log series K S0

Twenty-one Eats K S0 s: m-

s il4is_LA C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 44 575647 V. Description of the invention (41) Table 3

C: \ 2D-00DE \ 91-12 \ 91121999.ptd Page 45 575647 V. Description of the invention (42) Effect of the invention The latex-type adhesive composition of the present invention is manufactured by the specific steps described above, and is almost at the time of polymerization. No agglomerates are formed. In addition to excellent storage stability, its adhesion (especially adhesion to polyolefins), retention, adhesion to substrates, water resistance (especially to prevent hair from immersion in water) White properties) are excellent.

C: \ 2D-CODE \ 91-12 \ 91121999.ptd page 46 575647 Simple illustration of the drawing C: \ 2D-CODE \ 9M2 \ 91121999.ptd page 47

Claims (1)

575647— Announcement 1 _ 丨 丨 丨 16. The application method of I Congshi 1 will be made by (a kind of liqiqi, a type of adhesive composition manufacturing method, which is characterized by: succinic acid alkyl ester (a 1) is The main ingredient of ethyl cyanide is # 7 and monomer (A) and the oil-soluble component that is given to the technically-saturated medium 1). It is emulsified with 1 / C of water-granulated particles. The above-mentioned oil-soluble components are made flat: U &quot; 111 or less, thereby preparing an emulsion [I]; Resin: ί: 丨 Polymerize the emulsion ⑴ to obtain 1 f tree gum [丨 丨] In the presence of a polymer, an ethylenically unsaturated monomer (E) polytype adhesive composition containing alkyl (meth) acrylate β) as a main component will be used.亍 』孔 心 2. For example, the manufacturing method of the latex-type adhesive composition according to item 丨 of the patent application = method, wherein the ethylenically unsaturated monomer (E), in addition to (meth) propylene &amp; C alkyl ester In addition to (e 1), an unsaturated monomer (e 2) having a carboxyl group is also contained. 3. The method for producing a latex-type adhesive composition according to item 2 of the patent application, wherein the content of the unsaturated monomer (e2) with a carboxyl group is 1 to i relative to the ethylenically unsaturated monomer (E). 〇wt%. 4. The method for manufacturing a latex-type adhesive composition according to item i of the application, wherein the ethylenically unsaturated monomer (E) contains a (meth) acrylic acid alkyl ester (el) and a tape Unsaturated monomer (e2) having carboxyl group and unsaturated monomer (e3) having parentable group (but not including unsaturated monomer (e2) having carboxyl group). 5. The method for producing a latex-type adhesive composition according to item 4 of the scope of patent application, wherein the content of the unsaturated monomer (e 2) having a carboxyl group is 1 to 1 with respect to the ethylenically unsaturated monomer (E). 10% by weight, unsaturated with crosslinkable groups C: \ 2D-CODE \ 91-12 \ 91121999.ptd Page 48 575647 VI. Patent application scope monomer (e3) (but excluding unsaturated monomer (e2) with carboxyl group) content is 0. 0 5 ~ 5 wt% 〇6. The method for producing a latex-type adhesive composition according to item 4 of the patent application, wherein the unsaturated monomer (e 3) having a crosslinkable group (but not including the carboxyl group-containing unsaturated monomer) The saturated monomer (e2)) is an unsaturated monomer containing a ketone group. 7. The method for manufacturing a latex-type adhesive composition according to item 1 of the patent application scope, wherein the above-mentioned latex-type adhesive composition further comprises a cross-linking agent (F). 8. The method for producing a latex-type adhesive composition according to item 7 of the scope of patent application, wherein the cross-linking agent (F) is selected from the group consisting of degraded diimines, oxazoline compounds, and ethyleneimines A compound and at least one of a hydrazine compound. C: \ 2D-CODE \ 9M2 \ 91121999.ptd Page 49