JPS5811909B2 - adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition mainly for paper, which has improved properties such as thixotropic properties, water retention properties, and initial adhesion properties.

Adhesives or sizing agents for cardboard, mounts, bag making, paper tubes, etc. are conventionally made using (a) natural products such as starch, (b) semi-synthetic water-soluble polymers such as carboxymethylcellulose or methylcellulose, and (c) polyvinyl. alcohol, polyacrylic acid soda,
For the sole use of synthetic water-soluble polymers such as polyethylene oxide, formulations in which clay minerals and boric acid are blended with polyvinyl alcohol have been proposed.

However, the above methods (a) and (b) are susceptible to rotting and mold growth, and are also problematic in terms of adhesiveness and stability of the glue solution.

Sodium polyacrylate (c) has poor stability with respect to inorganic clay and has a flocculation-sedimentation effect, and polyethylene oxide has poor solubility in water and is unstable.

Polyvinyl alcohol-only adhesives have a high water content, and if used with poor drying equipment, the initial adhesion strength will be poor.

Next, the formulation in (2) aims to reduce the cost of the size agent and improve its adhesion to rough surfaces, but in such a system, especially when the paper is dry, the size Penetration speed is high and bonding defects are likely to occur.

Especially recently, due to cost reduction, the size has been reduced,
Because it is difficult to obtain softwood, the paper quality tends to be poor, and as a result, the rate of penetration becomes faster and poor lamination is likely to occur.

In addition, the clay minerals to be removed include bentonite, which gives the sizing agent anti-sag properties and thixotropic properties.
It is limited to water-swellable clays such as montmorillonite clay and chlorite clay, and the use of non-swellable kaolin or low-cost acidic clays has the disadvantage of poor performance as a sizing agent.

The present invention has solved the above-mentioned conventional difficulties, and the adhesive composition of the present invention can be prepared by homopolymerizing vinyl acetate monomer, or by copolymerizing the vinyl acetate monomer with 50 mol% or less of other monomers that can be copolymerized. Polyvinyl alcohol resin (A) obtained by saponifying 50 to 100 mol% of vinyl acetate resin obtained by copolymerizing with
100 parts by weight Clay mineral (B) 30-400 parts by weight 1 copolymer of polyalcohol poly(meth)allyl ether and (meth)acrylic acid or (anhydride) maleic acid (C) 0.2-20 parts by weight Boron It consists of 0 to 20 parts by weight of acid or borax (D), and has the following remarkable effects.

(1) Even under dry conditions or if the paper quality is poor, problems such as poor lamination due to excessive penetration of the adhesive into the paper will not occur.

(2) Dragging during application of glue can be effectively prevented, improving work efficiency.

(3) The lamination speed can be improved.

(4) Non-swellable kaolin can be used, and inexpensive acidic clay can also be used.

(5) Stringiness can be prevented and workability during application can be improved.

The polyvinyl alcohol resin (A) in the present invention
Polyvinyl acetate Saponified polyvinyl alcohol with about 50 to 100 mol%, or vinyl acetate as the main component, and other monomers that can be copolymerized with up to 50 mol%, such as olefins (ethylene, propylene, α-butene, α−
octene, α-dodecene, α-octadecene), unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, etc.) or their esters or salts, unsaturated polycarboxylic acids (maleic acid, fumaric acid, itaconic acid, etc.) acids, etc.) or their partial or complete esters or salts or anhydrides, unsaturated sulfonic acids (ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, etc.) or their salts, amides (acrylamide, methacrylamide, etc.), nitriles ( acrylonitrile, methacrylonitrile, etc.)
, vinyl ether, vinyl ketone, vinyl chloride, etc., which is obtained by saponifying 50 to 100 mol% of vinyl acetate resin.

The above-mentioned polyvinyl alcohol resins include those modified by acetalization, urethanization, phosphoric acid esterification, cyanethylation, or grafting of vinyl monomers to the extent that the effects of the present invention are not lost.

From a structural point of view, clay minerals (B) include pyrophyllite, sericite, illite, celadonite, and glauconite, which are three-layered pyrophyllite derivatives.

The brittle mica group includes margarite, xanthophyllite, and stilpnomerene.

Talc derivatives include talc and minnesotaite.

The montmorillonite group includes montmorillonite, nontronite, beidellite, saponite, and hectorite.

In the three-layered or two-layered chlorite group, the orthochlorites include click roll, pennin, and amesite.

Leptochlorites include afrosibrite, thuringite, chamosite, telesite, diapantite, and cronstedite.

Two-layered kaolin minerals include kaolinite, anoxide, nacrite, and delight.

Among halloysites, halloysite, hydrated halloysite,
Allophane.

The serpentine group includes antipolide and greenalite.

Multi-chain structure type In the serpentine group, chrysotile and serpentine.

Sepiolite, attapulgite, and paramontmorillonite in the palygorskite group.

etc. are used.

Next, from a usage standpoint, clay, add-on, alluvial clay, alluvial soil, ball clay (plastic clay), bauxite clay,
bentonite, bonded clay, flagstone clay, brick clay, valley clay, calcareous clay, china clay, intussusception clay, delta clay, diamepore clay, silica clay, estuarine clay,
Fireclay, filling clay, flint clay, Honghuan sedimentary clay, molding clay, acid clay, gumbo clay, gumbochil, kaolin, lake bed clay, raking, loam, loess, seabed clay, modeling clay, papermaking clay, Residual clay, rubber clay, sagger clay, sedimentary clay, semi-flint clay, shale clay (sierre), silicic clay, top clay, pottery clay, surface clay, terracotta clay, terrace clay, base clay, striped clay , Moejo, etc.

In terms of production, acid clay, slip clay, bleached clay, clear clay, porous clay, aqueous clay, high alumina clay, marl, micaceous clay, waxite, kibushi clay, frog's eye clay, and Kira etc. can be mentioned.

Typical clays are shown along with their production areas: Among fireclays, hydrothermal clay...Gunma Joshin deposit, Mt.Azuma, shale clay...Iwate deposit, Kitakami production area, Frogme clay・・・・・・
・Gifu Toki deposit, Tokiguchi pottery layer, Kibushi clay...
Aichi Seto deposit, Seto clay layer, weathered residual acid clay...
・Fukuoka Yame deposit ・Hemeshiro clay layer, hydrothermal deposit of kaolin...Yamagata Itaya kaolinitic clay, sedimentary deposit...Georgia kaolin in the United States, waxite Pyrophyllite waxite...Hiroshima Katsumitsuyama deposit, kaolinite waxite...Hyogo Kagawa deposit,
Sericitic waxite...Okayama Yagi deposit, pottery stone...
...Saga Arita Yamakawa deposit, sericite clay...
Examples include the Shimane Iishi Santoya deposit, acid white clay, the Niigata Itoigawa deposit, and the bentonite Gunma Toyojun deposit.

When using alkaline clay minerals such as bentonite and chlorite clay, it is desirable to simultaneously add an appropriate amount of oxalic acid or other acids, and it is particularly preferable to use powdered acids.

The reason is to suppress extreme water swelling.

Polyalcohol poly(meth)allyl ether and (meth)
Copolymer (C) with acrylic acid or (anhydrous) maleic acid
(Hereinafter, it will be abbreviated as copolymer (C).

The polyalcohol poly(meth)allyl ether of ) refers to divalent or higher valent allyl ether or methallyl ether of a polyalcohol having two or more, preferably three or more, hydroxyl groups in one molecule.

Examples of polyalcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, 1,2,3-butanetriol, glycerin, diglycerin, 3-methylpentane-1,3, 5-triol, 2,3,4-trihydroxybutyric acid, aldohexose, ketopetose, aldopentose, ketopentose, aldohexose, ketohexose, sucrose, maltose, lactose, raffinose, hexozane, pentozan, galactosone, glucomanan, starch , pentaerythritol, dipentaerythritol, tripentaerythritol, arabitol, marnitol, iditol, tritol, sorbitol, inositol, dulcitol, etc., or reduced derivatives thereof, such as mono- and dicarboxylic sugar acids.

Among these, oligosaccharides, that is, sugars, reduction products of sugars (
alcohols, keto alcohols, alkoxy alcohols, etc.), sugar oxidation products (sugar acids, keto acids, aldo acids, etc.)
Preferred examples include glucose, galactose, fructose, sorbose, rhamnose,
Examples include sucrose, arabinose, maltose, lactose, and raffinose.

Etherification is obtained, for example, by reacting a polyalcohol with allyl halide or meta-allyl halide under strongly alkaline conditions.

Polyalcohol poly(meth)allyl ether, (meth)
The inclusion of other comonomers in addition to the monomers of acrylic acid and maleic acid (anhydride) does not pose any particular problem.

Examples of such comonomers include α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, sorbic acid,
Itaconic acid, citraconic acid, mesaconic acid, muconic acid, glutaconic acid, aconitic acid, cinnamic acid, α-phenylacrylic acid, fumaric acid, and their salts, anhydrides in the case of polyvalents, styrene monomers, acrylamide , methacrylamide, acrylonitrile, methacrylonitrile, acrylic ester, methacrylic ester, vinyl ester, vinyl ether, vinyl ketone, vinyl chloride, vinylidene chloride, vinylpyrrolidone, ethylene, α-
Examples include olefins and maleic acid diesters.

The content of polyalcohol poly(meth)allyl ether in the copolymer (C) is selected from the range of 0.01 to 30% by weight, but 0.01 to 10% by weight is actually sufficient.

If its content is too small, the addition effect will not be achieved, while if its content is too large, it will lose its affinity for water, making it unsuitable for use in adhesives.

On the other hand, the content of (meth)acrylic acid or (anhydrous) maleic acid in the copolymer (C) is 25% by weight or more, preferably 40% by weight or more.
It is sufficient that the amount is at least % by weight, and the remainder can be supplemented with other comonomers as described above.

If the content of the above-mentioned compound is less than 25% by weight, the affinity with the polyvinyl alcohol resin decreases, and therefore the effect of improving the viscosity of the aqueous solution is significantly impaired.

Next, as the boric acid or borax (D), boric acid is particularly preferably used, but borax may be used without any problem.

The blending amounts of each component per 100 parts by weight of the polyvinyl alcohol resin (A) are: 30 to 400 parts by weight of clay mineral (B), 0.2 to 20 parts by weight of copolymer (C), and boric acid or borax. (D) is selected from the range of 0 to 20 parts by weight.

If the amount of component (B) is less than this, the adhesive strength will be poor when the object to be adhered has a rough surface, resulting in a disadvantage in terms of cost, and if it is too large, the adhesive effect will be poor.

If the amount of component (C) is less than this, the thixotropic properties and anti-sagging properties will be insufficient, if it is too much, the viscosity will be excessively thickened and it will be difficult to apply, and if it is even larger, the adhesive property itself will be inhibited, It will also be disadvantageous in terms of price.

Component (D) may be omitted, but when 2 to 20 parts by weight is added, the initial adhesive strength is improved.

However, if the amount exceeds 20 parts by weight, the coating properties will gradually deteriorate, and furthermore, the polyvinyl alcohol resin will gel and lose its adhesive strength.

A particularly preferable blending ratio is B to 100 parts by weight of (A).
) 60 to 300 parts by weight, (C) 1 to 15 parts by weight, (D)
The composition contains 15 parts by weight or less.

Each of the above components (A), (B), (C), and (D) is dissolved or dispersed in water and adjusted to a solid content concentration of about 1 to 40% by weight, and used for cardboard, mount, bag making, etc. It can be suitably used as an adhesive or paste for paper tubes, etc.

It can also be used to bond wooden products such as plywood, and materials other than paper such as woven and non-woven fabrics.

Note that suitable additives such as other water-soluble polymers, colorants, fibers, antifoaming agents, and foaming agents can be added to the adhesive composition of the present invention, if necessary.

Next, the composition of the present invention will be further explained by giving examples.

Hereinafter, "parts" and "%" are expressed on a weight basis unless otherwise specified.

Polyvinyl alcohol resin (A) used: Polyvinyl alcohol A-1 with degree of polymerization of 1800, degree of saponification of 88.0 mol%, polyvinyl alcohol A-2 degree of polymerization of 500, polyvinyl alcohol A-3 with degree of saponification of 88.0 mol%, degree of polymerization of 1700. , obtained by saponifying 94.1 mol% of the vinyl acetate component of polyvinyl alcohol A-4 with a saponification degree of 96.0 mol% and a monomethyl maleate-vinyl acetate copolymer with a monomethyl maleate content of 2.2 mol%. Degree of polymerization: 1700
Polymerization degree 25 obtained by saponifying 98.0 mol% of the vinyl acetate component of the monomethyl maleate-modified polyvinyl alcohol A-5 allylsulfonate sodium content 2.0 mol% vinyl acetate copolymer
Sodium allylsulfonate modified polyvinyl alcohol A-6 Clay mineral (B) using polyvinyl alcohol with a degree of polymerization of 800 and a degree of saponification of 99.2 mol% B-1 Fujirite Kogyo Co., Ltd. Special Moon Seal, Kaolin series, Okayama Prefecture Wake-gun Yoshinaga deposit, pH 5.0, grain size 1.0μ B-2 Showa Mining Co., Ltd. Suwanee, chlorite (chloride group, pennine series), Wanibuchi deposit, Kawashita-cho, Hirata City, Shimane Prefecture, pH 7.2, grain size 2μ B-3ASP-600, imported, kaolinite, Georgia, USA, pH 4.2, particle size 0
．． 8μ B-4 Showa Mining Co., Ltd. Silky, waxite clay (pyrophyllite), Katsumitsuyama deposit, Yokitamachi, Shobara City, Hiroshima Prefecture, p
H5,5, particle size 15 μB-5 Toyojun Yoko Hotaka Sein,
Bentonite type (montmorillonite), Yokoyo, Matsuida-cho, Usui-gun, Gunma Prefecture, PH9.8, particle size 40μ Copolymer used (C) C-1 acrylic acid-allyl sucrose (weight ratio 97:3) copolymer, but allyl The number of allyl groups in one molecule of sucrose is 5.6 C-2 acrylic acid-allyl pentaerythritol (weight ratio 93 nia) copolymer, however, the number of allyl groups in one molecule of allyl pentaerythritol is 2.8 C-3 acrylic acid. Acid-allyl sorbitol (weight ratio 95:
5) Copolymer, however, the number of allyl groups in one molecule of allyl sorbitol is 4.7. Sodium acrylate allyl sucrose copolymer C-5C-1, which is obtained by neutralizing a C-4C-1 copolymer with sodium hydroxide. Ammonium acrylate-allyl sucrose copolymer C-6 methacrylic acid-styrene-allyl sucrose (weight ratio 4)
3:56:1) copolymer, however, the number of allyl groups in one molecule of allyl sucrose is 5.2 C-7 acrylic acid-vinyl acetate-allyl sucrose (weight ratio 75:23.5:1.5) copolymer Combined, but 5.8 allyl groups in one molecule of allyl sucrose C-8
Maleic anhydride-vinyl n-butyl ether-methallyl sucrose (weight ratio 50:49.5:0.5) copolymer, however, 5.5 metaallyl groups in 1 molecule of methalyl sucrose C' Polyacrylic acid as a control example soda boric acid,
Boric acid (D) D-1 Boric acid D-2 Borax Examples 1 to 14, Control examples 1 to 9 Each of the following components by weight A:B:C:D=55:45:3:
A paste having a solid content concentration of 18% was prepared by adding it to water and stirring with heating.

The stability, apparent viscosity, and thixotropic index of this size solution were investigated, as well as the initial adhesive strength to liner paper, pot life to medium-quality paper, and degree of sag.

The results are shown in Table 1.

Examples 15-23, Control Examples 10-13 The following components by weight: A:B:C:D=50:50:3:
A paste having a solid content concentration of 18% was prepared by adding it to water and heating and stirring.

When B-5 was used as a guide component, oxalic acid was further blended at a ratio of 0.5 to B50.

Claims (1)

[Claims] 1. A vinyl acetate resin obtained by homopolymerizing a vinyl acetate monomer or copolymerizing the monomer with 50 mol% or less of another copolymerizable monomer.
0 mol% saponified polyvinyl alcohol resin (A)
100 parts by weight clay mineral (B)
30-400 parts by weight Copolymer of polyalcohol poly(meth)allyl ether and (meth)acrylic acid or (anhydride) maleic acid (C) 0.2-20 parts by weight Boric acid or borax (D) 0- An adhesive composition comprising 20 parts by weight.