JPS6166773A - Adhesive composition - Google Patents

Abstract

PURPOSE:To produce the titled composition having excellent bactericidal and fungicidal properties, by polymerizing a conjugated diene monomer, an aromatic vinyl monomer, a specific vinylimidazole derivative and other polymerizable monomer at specific ratio, and using the obtained copolymer as an essential component. CONSTITUTION:(A) 20-80(wt)% conjugated diene monomer (e.g. 1,2-butadiene), (B) 19.8-75% aromatic vinyl monomer (e.g. styrene), (C) 0.2-10% vinylimidazole derivative of formula (R1-R4 are H, 1-12C alkyl or phenyl; X is H or halogen) and (D) 0-50% other polymerizable monomer (e.g. methyl methacrylate) are polymerized together, and the obtained copolymer is used as a component of the objective adhesive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] The present invention relates to an adhesive composition having excellent antibacterial and antifungal properties.

More specifically, it is characterized by containing a copolymer obtained by polymerizing a specific derivative and various monomers, and has excellent antibacterial, antifungal and antifungal properties, and is suitable for use in carpet backing, nonwoven fabrics, and coating. The present invention relates to an adhesive composition that can be used as a binder for paper and paint, and other adhesives.

In recent years, the amount of carpet used has been increasing because it provides a comfortable living environment in terms of interior design, livability, heat retention, etc. On the other hand, Japan's climate is quite hot and humid depending on the season, which can cause mold and bacteria to grow on carpets. Bacteria,
Methods such as mixing antifungal agents into adhesive compositions, applying them to carpet fibers, or impregnating them into carpet fibers are known. However, these methods require many manufacturing steps and are difficult to use in the working environment. , it has the disadvantage of worsening.

In addition, these methods do not exhibit the characteristics of the polymer, resulting in deterioration of various objects, and furthermore, the adhesion to objects also decreases, so they also have the disadvantage that wash resistance cannot be obtained.

As a result of intensive research in view of such problems, the present inventors found that
The present invention was achieved by discovering that a composition containing a copolymer obtained by polymerizing a specific derivative and various monomers has excellent antibacterial and antifungal properties.

Since the copolymer used in the present invention has a vinylimidazole derivative bound thereto, it exhibits the characteristics of a polymer. For example, the copolymer has improved water resistance after processing, and since there is almost no desorption due to washing CH=CH2, the washing resistance is improved.

In addition, since the copolymer is cationically charged,
Adhesion and adhesion to negatively charged objects such as cellulose, inorganic pigments, and adherends are improved.

Furthermore, if necessary, a cationic antibacterial/antifungal agent can be used in the copolymer.

When using a cationic antibacterial/antifungal agent in the copolymer, there is no need to stabilize it with a cationic emulsifier, etc., so it is not necessary to stabilize it with a cationic emulsifier. There is no deterioration in physical properties, and superior processing properties can be obtained compared to conventional products. ' [Structure of the invention] That is, the present invention comprises conjugated diene monomers of 20 to 80% by weight,
Aromatic vinyl monomer 19.8-75% by weight, following general formula (I) Group or phenyl group X: Vinylimidazole derivative represented by hydrogen or halogen 0.2-10% by weight 1
%, and a copolymer obtained by polymerizing 0 to 50% by weight of other polymerizable monomers. .

0 Conjugated diene monomers The conjugated diene monomers used in the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene, ° ゛=±#1-chloro-1
．． 3-butadiene, 2-chloro-1,3-butadiene,
Substituted linear conjugated pentadines, conjugated hexadienes with linear and side chains These monomers are used in amounts of 20 to 80% by weight, but if less than 20% by weight, low temperature flexibility decreases and
If the amount exceeds % by weight, the adhesion will decrease.

These monomers can be used alone or in combination of two or more.

0 Aromatic vinyl monomer Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, dimethylstyrene, chlorostyrene, and vinyltoluene.

These monomers are used in an amount of 19.5 to 75% by weight, but if the ratio is less than 19.5:i, adhesiveness decreases and 75'N
If the amount exceeds 0, the low temperature flexibility decreases.0 These monomers can be used alone or in combination of two or more.

O Vinylimidazole derivative The vinylimidazole derivative used in the present invention has the following general formula (I) CH=CH2 t group or phenyl group 1-methylimidazole chloride, 1-vinyl-2,3
-dimethylimidazole chloride, 1-vinyl-2,
3,4-trimethylimidazole chloride, 1-vinyl-2-ethyl-3,4-dimethylimidazole chloride, ■-vinyl-2-ethyl-3-methylimitasole chloride, 1-vinyl-2-phenyl-3-methylimidazole Chloride, 1-vinyl-2-dodecyl-
3-Methylimidazole, 1-vinyl-3-methylimidazole bromide, 1-vinyl-2,3-dimethylimidazole bromide, 1-vinyl-2-ethyl-3-
Methylimidazole chloride, 1-vinylimidazole hydrochloride, 1-vinyl-3-ethylimidazole chloride, 1-vinyl-3-propylimidazole chloride, 1-vinyl-3-butylimidazole chloride, 1-vinyl-3-hexylimidazole chloride , 1-vinyl-3-octylimidazole chloride, 1-vinyl-3-decylimidazole chloride, 1-vinyl-3-dodecylimidazole chloride, and the like.

does not improve, and is economically unfavorable.

These derivatives can be used alone or in combination of two or more.

Other polymerizable monomers used in the present invention include vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, and unsaturated monomers containing hydroxyalkyl groups. Examples include monomers having other unsaturated vinyl bonds, such as vinyl chloride, vinylidene chloride, and vinyl acetate.

Examples of vinyl cyanide monomers include acrylonitrile,
Examples include methacrylonitrile.
＼Unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, cyclohexyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fluorate, diethyl maleate,
Diethyl maleate, dimethyl itaconate, trimethyltin acrylate, triethyltin methacrylate, triethyltin acrylate, triethyltin methacrylate, tri)tin acrylate, triethyltin methacrylate, tributyltin acrylate, tributyltin methacrylate, triiso Examples include pentyltin acrylate, triisopentyltin methacrylate, tri-n-hexyltin acrylate, and tri-n-hexyltin methacrylate.

Monomers containing hydroxyalkyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, (ethylene glycol) itaconate 1. ;;-(Propylene glycol) itaconate, bis(2-hydroxypropyl) itaconate, bis(2-hydroxyethyl) itaconate, bis(2-hydroxyethyl) fluorate, bis(2-hydroxyethyl) malate, 2-hydroxyethylmethyl Examples include fumarate, 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ketone, allyl alcohol, and the like.

Other monomers having unsaturated vinyl bonds include 2
-vinylpyridine, 5-ethyl-2-vinylpyridine,
2-methyl-5-vinylpyridine, 4-vinylpyridine, N-methylol.

Examples include acrylamide, acrylamide, methacrylamide, (diethyl)aminoethyl acrylate, and (diethyl)aminoethyl methacrylate.

These monomers are used at 0 to 50% by weight, but 5O
If the amount of N exceeds 1, the adhesion and low-temperature flexibility will decrease.

These monomers can be used alone or in combination of two or more.

0 Polymerization Methods for obtaining the copolymer used in the present invention include generally known emulsion polymerization methods, suspension polymerization methods, and solution polymerization methods.

Note that there are no particular restrictions on the method of adding the various components in 1 go, and any of the initial batch addition method, divided addition method, and continuous addition method may be used, and furthermore, generally known multi-stage polymerization methods may be used. can.

0 Mixture Generally known fillers, dispersants, plasticizers, anti-aging agents, etc. can be used in the adhesive composition of the present invention.

The present invention will be specifically explained below using Examples, but the present invention is not limited by these in any way.

Note that parts in this example mean parts by weight. [Example] 0 Copolymer Latex A In a pressure container, 122 parts of ion-exchanged water, 3 parts of nonionic emulsifier, 2.2' azobis(2-aminodipropane) ) Hydrochloride 0
．． 4 parts were added and stirred, and then 50 parts of butadiene, 37 parts of styrene, 10 parts of methyl methacrylate, and 1-vinyl-
A mixture of 3 parts of 3-methylimidazole chloride and 0.2 parts of dodecyl mercaptan was added thereto. The temperature was raised to 75° C. with stirring, and polymerization was carried out for 15 hours.

Unreacted monomers from the obtained copolymer latex were removed by stripping to obtain copolymer latex A.

0 copolymer latex B In a pressure container, 122 parts of ion exchange water, 3 parts of nonionic emulsifier, 2.2' azobis(2-aminodipropane) hydrochloride 0
．． 4 parts, 1 part of 1-vinyl-2,3-dimethylimidazole chloride was added, and further 20% of a mixture consisting of 45 parts of butadiene, 42 parts of styrene, 12 parts of methyl methacrylate, and 0.2 parts of dodecyl mercaptan was added, and the mixture was stirred. Polymerization was started by raising the temperature to 75°C.

The remaining mixture was then added continuously over a period of 6 hours.

When the polymerization rate exceeded 98%, one part of a nonionic emulsifier was added, and unreacted monomers of the resulting copolymer latex were removed by stripping to obtain copolymer latex B.

0 Copolymer Latex C In a pressure-resistant container, 122 parts of ion-exchanged water, 3 parts of nonionic emulsifier, 2.2 azobis(2-aminodipropane) salt R salt 0.
4 parts, 3 parts of 1-vinyl-2-ethyl-3-methylimidazole chloride were added, and further 20% of a mixture consisting of 55 parts of butadiene, 29 parts of styrene, 10 parts of methyl methacrylate, and 0.2 parts of dodecylmercaptan was added. The temperature was raised to 75° C. under stirring to initiate polymerization. Polymerization rate is 6
When it reached 0%, a mixture of the remaining mixture and 3 parts of 1-vinyl-2-ethyl-3-methylimidazole chloride was added over 6 hours to further polymerize.

When the polymerization rate exceeded 98%, 1 part of a nonionic emulsifier was added, and unreacted monomers of the resulting copolymer texose were removed by stripping to obtain copolymer latex C.

0 copolymer latex D to H Copolymer latex A was added to styrene-butadiene copolymer latex containing no preservative so that the amount of 1-vinyl-3-methylimidazole chloride was as shown in Table 1. By mixing, a copolymer latex DH was obtained.

Pseudomonas (
A 1% solution containing 108 Pseudomonas bacteria per ml was added and maintained at 35 to 40°C. The bacterial counts were measured one week and one month later and are shown in Table 1.

Next, 2y (solid content) of each of the copolymer latexes A-C'i and physiological saline in the same volume as the copolymer latex were added to a solution 4 containing 4.2 x 10' Pseudomonas bacteria per Nll. Mixed with ml. The number of bacteria was measured after being left for 2 hours and is shown in Table 2.

Table-1 Table-2

Claims (1)

[Claims] Conjugated diene monomer 20 to 80% by weight, aromatic vinyl monomer 19.8 to 75% by weight, the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ ( I) However, R_1 to R_4: hydrogen, an alkyl group having 1 to 12 carbon atoms, or a phenyl group An adhesive composition comprising 50% by weight of a copolymer obtained by polymerization.