JPS63314221A - Production of emulsion - Google Patents

Abstract

PURPOSE:To obtain an emulsion excellent in ink transfer, surface strength, etc., of a coated paper and useful as, e.g., a binder or an adhesive in paper coating and textile processing, by emulsion-polymerizing an aliphatic conjugated diolefin with four specified monomers. CONSTITUTION:An emulsion of a particle diameter of 0.05-1mum and a solid content of 40-65% is obtained by emulsion-polymerizing 10-90wt.% 4-5C aliphatic conjugated diolefin (A) (e.g., 1,3-butadiene), 0.5-20wt.% ethylenically unsaturated carboxylic acid monomer (B) (e.g., itaconic acid), 0.5-20wt.% ethylenically unsaturated amine monomer (C) (e.g., dimethylaminoethyl methacrylate), 0.5-20wt.% monomer (D) of the formula (wherein R1 is H or CH3, R2 is a 1-3C alkylene, and R3 is a 1-4C alkyl), e.g., N-n- butoxymethylacrylamide, and 0-88.5wt.% monomers (E) copolymerizable therewith (e.g., styrene) at 30-100 deg.C in an aqueous dispersion in the presence of an emulsifier and a polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Fields) Polymer emulsions are used in a wide range of fields such as adhesives and paints. The polymer emulsion of the present invention can also be used in such fields, particularly as an inder in paper coating and fiber processing, or as a general adhesive.

BACKGROUND OF THE INVENTION Currently, large amounts of pigment-coated paper are used for publications and packaging. The purpose of pigment coating is primarily to impart excellent printability to paper and increase its commercial value as printed matter. In this field, carboxy-modified styrene-butadiene emulsions have been most commonly used as pigment binders. Coated paper using a carboxy-modified styrene-butadiene emulsion has excellent properties in terms of surface strength and gloss. However, in recent years, the coating speed in the coated paper manufacturing process has increased. Also, as printing speeds increase, problems have arisen in print suitability such as transferability of ink to coated paper and pinking resistance due to pigment binding force Vcff1 of emulsion.Solving these problems Therefore, various studies have been conducted on the composition of pigments and adhesives that make up the coating liquid.In view of this situation, various studies have been conducted regarding pigments, materials, and polymer emulsions as 6-inders. Improvements have been made.

For example, Japanese Patent Publication No. 61-39334 discloses a conjugated diolefin copolymer latex obtained by emulsion polymerization of an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated amine monomer under conditions where they do not coexist with each other. It has been disclosed that the surface strength and ink transfer properties of coated paper and the strength of carpets, nonwoven fabrics, etc. can be improved using the same.

Also known are a method of emulsion polymerization of a monomer containing an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated amine in the presence of an amphoteric emulsifier, and a method of mixing an amine-modified water-soluble compound with latex. However, although these methods do improve the ink transfer properties and the wet strength of the coated paper surface, in order to obtain sufficient ink transfer properties, it is necessary to reduce the surface strength of the coated paper. It has disadvantages such as inviting Furthermore, JP-A-61-275497
In the presence of an amphoteric emulsifier, an aliphatic conjugated diene compound,
Emulsion polymerization of ethylenically unsaturated carboxylic acids, ethylenically unsaturated amines, copolymerizable unsaturated compounds containing amide bonds, unsaturated carboxylic acid esters containing hydroxyl groups, and monomers copolymerizable with these at pH 6 or higher. A composition for coated paper using a copolymer latex obtained as a coating material is disclosed. However, this invention
When a pigment mainly composed of fine grained ground calcium carbonate having a specific particle size distribution is used, coated paper with particularly good paper surface smoothness can be provided. Attempts to improve the transferability of the ink lead to a decrease in the surface strength of the coated paper, which remains an unresolved problem.

Styrene-butadiene emulsions are also commonly used as inders for fiber processing. When using adhesives for carpent backing, there is often a problem with the formation of so-called blisters, which cause bulges on the surface of the carpent when water in the adhesive applied to the carpent evaporates during the carpet drying process. The occurrence of blisters not only significantly impairs the appearance of the carpet, but also causes a decrease in peel strength. Furthermore, in recent years, in order to improve productivity in carpet manufacturing, high-speed drying at high temperatures and large air volumes has become commonplace, and due to the shortage of jute fabrics, the next base fabric has been replaced with polypropylene fibers, which have poor breathability and water absorption. It is transitioning. For this reason, conditions have become more likely to cause blisters. For this reason, various studies have been made on latex additives and adhesive compositions, but none of them have achieved satisfactory performance, and further improvements are desired.

(Problems to be Solved by the Invention) As described above, these conventional techniques do not necessarily have fully satisfactory performance. That is, in coated paper applications, it has not been possible to simultaneously satisfy both the ink transfer or ink receptivity and the surface strength of the coated paper. Also, for carpet lining applications,
At present, drying conditions have been strengthened to improve productivity, but at present it has not been possible to prevent blistering and improve peel strength.

The present invention achieves extremely good performance in the properties that could not be satisfied at the same time in the past, such as ink transferability, surface strength of coated paper, improvement of carpet productivity, blister prevention property, and peel strength as described above. The present invention relates to a polymer emulsion having the following properties.

(Means for Solving the Problems) The present invention comprises 10 to 90% by weight of aliphatic conjugated diolefin and 0.5 to 2% by weight of ethylenically unsaturated carboxylic acid monomer.
0% by weight, 0.5 to 20% by weight of an ethylenically unsaturated amine monomer, 0.5 to 20% by weight of a monomer represented by the structural formula (1), and if necessary, a radical polymerizable monomer. The present invention relates to a method for producing a polymer emulsion characterized by copolymerizing 0 to 88.5 weight percent of other monomers by emulsion polymerization.

(几l is a hydrogen atom or a methyl group, 8yuki has 1 to 1 carbon atoms
(3) alkylene group, R3 is an alkyl group having 1 to 5 carbon atoms) The aliphatic conjugated diolefin provides the necessary flexibility to the copolymer.
are used. Specific examples of these include engineering, 3
-butadiene, pentagene, chloroprene, etc. The aliphatic conjugated diolefin has, for all monomers,
10 to 90 ik1 is used, preferably 20
The range is from 70% by weight, more preferably from 25 to 60% by weight. The amount of aliphatic conjugated diolefin is 103:
If the fi coefficient is less than 90% by weight or exceeds 90% by weight, the adhesive strength as a No. 9 inder decreases, which is not preferable. The ethylenically unsaturated carzenic acid monomer is an essential component for increasing the colloidal stability and adhesive strength of the emulsion. The amount used is from 0.5 to 20% by weight, preferably from 1 to 10% by weight. The amount used is 0.
5 weight: If it is less than 1ic4, it is difficult to provide the necessary colloidal stability, and if it exceeds 201ii%, water resistance will decrease and the viscosity of the emulsion will become extremely high, making it difficult to handle. becomes. Specific examples of ethylenically unsaturated acid monomers include acrylic acid, methacrylic acid, 7
Examples include mono- or dicarzenic acids such as maric acid, itaconic acid, and maleic acid, or acid anhydrides or monoalkyl esters of dicarzenic acids. The amount of ethylenically unsaturated amine is from 0.5 to 20% by weight, preferably from 0.5 to 10% by weight. If O15% by weight is 15% by weight, it is difficult to achieve the objectives of the present invention such as printability or anti-sister properties, and if it exceeds 20% by weight, the viscosity of the emulsion becomes extremely high and the adhesive strength decreases. invite Specific examples of ethylenically unsaturated amines include methylaminoether (aminoalkyl esters of ethylenically unsaturated carzenes such as methane acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate), methylamine ethyl (
meth) acrylamide, dimethylaminoethyl (meth)
Examples include aminoalkylamides of ethylenically unsaturated carzenic acids such as acrylamide P1 dimethylaminopropyl (meth)acrylamide, and alkenylpyridines such as 2-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine. . In addition to this, the monomer represented by formula (1) is essential in the production method of the present invention.

(1) In the formula, R2 is a hydrogen atom or a methyl group, preferably a hydrogen atom, R2 is an alkylene group having 1 to 3 carbon atoms, preferably a methylene group, and R3 is a methyl group having 1 to 5 carbon atoms. be. Specific examples where R1 is a hydrogen atom and R1 is a methylene group include N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-turopoxymethylacrylamide, N-isopropoxymethylacrylamide F, N-nbutoxymethylacrylamide, -ruacrylamide, N-5ee butoxymethylacrylamide P%N
-tertbutoxymethylacrylamide, N-inbutoxymethylacrylamide, N-n pentoxymethylacrylamide P, and the like. The amount of the monomer represented by formula (1) used is 0.5 to 20% by weight, preferably 1 to 10% by weight.

If it is less than 0.5% by weight, it will be difficult to achieve the object of the present invention, and if it exceeds 20% by weight, the fluidity of the emulsion will be poor, which is not preferable. As shown in Examples and Comparative Examples below, the compound represented by formula (1) exhibits a remarkable effect compared to acrylamide P, which is the most common unsaturated compound having an AND bond.

In addition to the above polymerized units, the polymer emulsion of the present invention has:
Other polymeric units, generally capable of radical polymerization, up to 8865 weight units may also be used. Examples of these monomers include:
Styrene, α-methylstyrene, 4-ethylstyrene,
4-niethoxystyrene, 3,4-dimethylstyrene, 2
-Hydroxymethylstyrene, 4-ethylstyrene, 4
- Aromatic styrene derivatives such as ethoxystyrene, 2-chlorostyrene, 4-chloro-3-methylstyrene, 2,4-dichlorostyrene, divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2- Acrylic esters such as ethylhexyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylonitrile,
Examples include vinyl cyanide monomers such as metacyclonitrile, amides such as acrylamide, methacrylamide, and N-methylolacrylamide.

Aliphatic conjugated diolefin monomers, ethylenically unsaturated carboxylic acid monomers, ethylenically unsaturated amine monomers, etc.
The monomers used in the present invention may be used alone or in combination of two or more monomers.

Next, a method for producing a polymer emulsion according to the present invention will be described.

The polymer emulsion in the present invention can be produced by a conventionally known emulsion polymerization method.

That is, in the aqueous dispersion system, ordinary heptadionic, nonionic, and cationic emulsifiers can be used as emulsifiers.

There is also no problem in using an amphoteric emulsifier. As the polymerization initiator, conventionally known initiators can be used, including persulfate, hydrogen peroxide, and redox-based initiators. The emulsifier and polymerization initiator may be added all at once at the initial stage, but generally they are added continuously.

There are also no particular restrictions on the chain transfer agent, and those conventionally known for use in emulsion polymerization can be used. There is no particular restriction on the temperature of the reaction, but it is usually preferably about 30°C to Zoo°C, more preferably 40°C to 80°C. There are no particular restrictions on the method of adding monomers, such as adding them all at once at the beginning, adding them continuously, or adding only a specific monomer all at once at the beginning or end of polymerization. , conventionally known methods are used. There is no problem in using a seed polymerization method commonly used in emulsion polymerization. There is no particular limit to the particle size of the emulsion, but it is usually 0.05 to 1μ,
Preferably it is 0.1 to 0.5μ. There are no particular restrictions on the solid content of the emulsion, but it is usually preferably 40 to 65 inches.

However, if an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated amine monomer are present at the same internal pressure in the polymerization system at a pH in the acidic range, which is the condition for normal emulsion polymerization, the polymerization stability generally becomes significantly lower. be damaged. For this purpose, a conventionally known method in which an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated amine monomer are polymerized under conditions where they do not coexist with each other, or in the presence of an amphoteric emulsifier, p) It is preferable to use a method such as carrying out emulsion polymerization under conditions of 16 or more. By adding various additives to the polymer emulsion produced according to the present invention, it may be used more preferably.

Examples of these are dispersants, disinfectants, viscosity modifiers, salts, etc. These may be added before, during, or after polymerization as necessary.
It can be added at any time after polymerization.

(Effects of the present invention) As mentioned above, the polymer emulsion of the present invention has excellent properties such as ink transferability and surface strength of coated paper that could not be satisfied simultaneously in paper coating applications. In addition, when used as a carpet backing adhesive, it significantly improves cyster resistance and peel strength even when drying conditions are strengthened to improve productivity. .

EXAMPLES The present invention will be further explained in detail with reference to Examples below, but it goes without saying that the present invention is not limited to these Examples in any way. In particular, unless there is a break, the number of copies listed below indicates the overlapping parts.

(Example-1) 20 parts of deionized water, 0.2 parts of sodium hydroxide, DOW
FAX 2A1 (manufactured by DOW Ohem, @) 0.1
1 part and 0.8 parts of sodium persulfate were mixed and dissolved, and the initiator water bath solution was poured into the solution.

Next, a monomer mixture containing 29 parts of sitadiene, 56 parts of styrene, 10 parts of methyl methacrylate, 3 parts of N-n butoxymethylacrylamide, and 8 parts of carbon tetrachloride was prepared.

An autoclave with a stirrer and internal volume of 11 was replaced with nitrogen, 70 parts of deionized water, and DOWFAX 2A10.08
part, itaconic acid and 2 parts of itaconic acid, and as seed particles, calzoxy-modified polystyrene emulsion (average particle size 0.
035μ, solid content 35%], 300
The internal temperature was raised to 80° C. while stirring at rpm. A monomer mixture solution and an aqueous solution prepared in advance were continuously and uniformly fed into this autoclave over 4 hours and 5 hours, respectively. During this time, the autoclave was 80
It was kept at ℃.

After the addition of the monomer mixture and the aqueous solution was completed, the internal temperature was raised to 90°C and the reaction was continued for 1 hour. Thereafter, residual monomers were removed by steam distillation, and a sodium hydroxide water bath was added to adjust the pH of the emulsion to 9.0. Next, dimethylaminoethyl methacrylate 2.
0 parts of ammonium persulfate and 0.1 parts of ammonium persulfate in 4 parts of deionized water.
and reacted at 80°C for 2 hours.

The particle size of the obtained emulsion was 0.18μ, and the polymerization rate was 9.
It was J39J. Let this emulsion be a latex person.

(Examples 2 to 5) Latex B to E were obtained in the same manner as in Example 1. These are collectively shown in the ailGi table.

(Comparative Examples-1 to 9) Latexes F to N were obtained in the same manner as in Example-1. These are also collectively shown in Table M1.

(Example 6) Using the obtained latex A-N, a paper making liquid was prepared according to the following recipe.

Coating liquid formulation Kaolinite clay (1) 80 parts heavy calcium carbonate (2) 20 parts dispersant (3)
0.3 Oxidized starch (4) 3 Latex (in solid content) 11 (1) Ultracoat, manufactured by gNGBLHA Risha (2) Niscalon #
2000. Sankyo! J! (3) Aron T-40. Made by Aron Kasei ■ (4) Egg Ace B, Oji Cornstarch ■
The total solid content of the coating solution was adjusted to 62%, and ammonia water was added.
The pH of the coating solution was adjusted to 9.5.

This coating solution was coated onto high-quality coating base paper using a blade-type continuous winding coater so that the coating amount was 13 g/ld on one side. The obtained coated paper was conditioned all day and night in a constant high and constant humidity room at 23°C and 50% humidity, and then heated at 60°C for 9w at 15%.
Sue/7-calender treatment was performed twice under the conditions of /cIi, and the following physical properties were measured.

The results are shown in Table 2.

(White paper gloss) According to Murakami type 0M-26D gloss meter F) 75'11-75°
Measured at

(Printability) Dry strength, wet strength, and ink receptivity were measured by conventional methods using a 几■ tester (Akashi Seisakusho) and an ink with excessive tack.

(Example-7) An adhesive composition was prepared according to the formulation shown below.

Prescription latex (in solids) 100 parts antifoaming agent (
1) O,tS heavy calcium carbonate (2) 400 (1) T8A
7341 Made by Toshiba Silicone (2) S 8-30
Made by Nitto Funka ■ Total solids content is 70% and viscosity is 18,000.
cps (B-type viscometer, No. 4 rotor, thickener (Viscomay) as appropriate to 12 rpm 9l-P4
60G) was added.

The obtained enclosing agent composition was applied to a tufted carpet whose base fabric was polyzolopyrene and whose pile was nylon at x, skp/m.
The mixture was applied uniformly at a ratio of 1.7 to 1.7, and a jute woven fabric was pressed to obtain an undried carpent. The following physical properties were measured for these carpents.

(Peel strength) Dry the carpent at 120°C for 20 minutes and remove the backing agent (1).
Peeling and strengthening, JI8 L-1021-1974r
It was measured according to the 'JC material test method'.

(Blister resistance) After drying the carpet at 160° C. for 10 minutes, the state of blistering of the thickener was observed with the naked eye.

2. The symbols in the table are ◎, ○, △, from good to good.
It is indicated by X. ◎ represents the extent to which no blisters were generated, and X represents the extent to which blisters were generated over the entire surface.

The above results are shown in Table 3.

, lcqgenll l I l dormitory ≧1 [phase] 81 agony 1 Tsukasa 1 guard &C″= 416 ro e;' l
Ig+mW
':4S Q, 11 g g I
oa vs m l l g
,,slggcfplw + , ,2= ,1■ Hei 1 Sen's 1 rumor ro c'4
To the second ship engineer Ro 1 Rumor day I N Lu = 6 (ga eQI 16ml
1 R-ni 26181 = Ji! mlhgc41 weight l M I
cps g2l:118! ! : ~ 1 唖 喰 I N
To Shigeru. 1g :: l oa red flag 1
Hesa = [嬌 @ Soyaku 舊] Table 2 Note: H, L, L, M cannot be measured because the fluidity of the coating fluid is not required. Table 3.

Claims (1)

[Claims] (1) 10 to 90% by weight of aliphatic conjugated diolefin;
Ethylenically unsaturated carboxylic acid monomer 0.5 to 20% by weight, ethylenically unsaturated amine monomer 0.5 to 20% by weight
% by weight, 0.5 to 20% by weight of the monomer represented by the general formula (I), and 0 to 88.5% by weight of other monomers copolymerizable with these monomers are emulsion polymerized. ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) (R_1 is a hydrogen atom or a methyl group, R_2 is an alkylene group having 1 to 3 carbon atoms, and R_3 is an alkyl group having 1 to 5 carbon atoms. )