JPH03122138A - Anchor coat agent for polypropylene - Google Patents

Abstract

PURPOSE:To obtain the title anchor coat agent for tacky tape, etc., consisting essentially of a specific water dispersed article of polyester resin and modified water dispersed article of polyester resin and modified water dispersed article thereof, free from danger of fire and improved in adhesion of barrier coat agent, etc. CONSTITUTION:The aimed anchor coat agent consisting essentially of (A) water dispersed article of polyester resin containing water soluble components of polyethylene oxide, carboxyl group, carbonyl group, amino group, methylcarbonyl group, carboxylic acid group, sulfonic acid group, sulfonic acid ester group, phosphoric acid ester and quaternary ammonium salt and having 2,000-30,0000 molecular weight and/or (B) water dispersed article obtained by modifying the component A with a compound having polymerizable double bond of 1-300 wt.% based on polyester resin.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to polypropylene fiber packaging, adhesive tapes, cut tapes, for vacuum deposition, and for food packaging such as frozen desserts, dried foods, oily foods, pickles, and fish paste products. This relates to anchor coating agents for films and polypropylene molded bodies.

[Conventional technology]

Conventionally, solvent-based chlorinated polypropylene and the like have been used as anchor coating agents for polypropylene films and molded products thereof.

Solvent-based anchor coating agents pose a risk of ignition during use, such as the occurrence of a fire, and therefore are limited in terms of usage management.

In addition, water-based anchor coating agents cannot be stored as anchor coated due to the adhesiveness of the dried film, and can only be used in in-line processes where top coating is applied immediately after processing.

The present invention was developed to solve these problems.

[Summary of the invention]

The anchor coating agent for polypropylene according to the present invention contains polyethylene oxide, carboxyl group, carbonyl group, amino group, methyl carbonyl group, carboxylate, sulfonate, sulfate ester salt, phosphate ester salt, quaternary Polyester resin aqueous dispersion (A
) and/or (A) with a compound having a polymerizable double bond in an amount of 1 to 300% by weight based on the polyester resin (B) is the main component.

The polyester resin used in the present invention has a glass transition point of 0 to 90°C, preferably 10 to 70°C, and has polyethylene oxide, a carboxyl group, a carbonyl group, an amino group, a methylcarbonyl group, or a carboxylic acid group in the molecule. It contains hydrophilic groups such as salts, sulfonates, lif acid ester salts, phosphate ester salts, and quaternary ammonium salts, and is a known polymer obtained by polycondensation reaction of dibasic saturated organic acid and diol. be.

Examples of polybasic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid,
Examples include sebacic acid, trimellitic acid, pyromellitic acid, dimer acid, etc., and one or more of them can be used.

Furthermore, together with these components, unsaturated polybasic acids such as maleic acid and itaconic acid, p-hydroxybenzoic acid, etc.
A small amount of hydroxycarboxylic acid such as (β-hydroxyethoxy)benzoic acid can be incorporated.

As a polyol component, ethylene glycol, 1.4
-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexane dimetatool,
Two or more of xylylene glycol, dimethylol 70 pionic acid, glycerin, trimethylolpropane, poly(ethylene oxide) glycol, poly(tetramethylene oxide) glycol, etc. can be used.

This polyester resin is dispersed and dissolved in water at 60 to 90oC to obtain a coating agent with a solid content of 20 to 40%.

Further, this aqueous polyester resin dispersion is modified by the method described below.

First, a polyester resin aqueous dispersion and a radical polymerization initiator, preferably an organic peroxide, are charged into a four-hole flask equipped with a reflux tube, and after thorough nitrogen purge, the temperature is heated at 45-95°C, preferably 60-95°C. A compound having a polymerizable double bond is added at 85°C to proceed with the reaction.

Compounds having polymerizable double bonds used here include vinyl esters, unsaturated carboxylic acid esters, unsaturated carboxylic acid amides, unsaturated nitriles, unsaturated carboxylic acids, allyl compounds, nitrogen-containing compounds, carbon (hydrogen or vinyl silane), A compound is used.

Vinyl esters include vinyl propionate, vinyl stearate, higher tertiary vinyl esters, vinyl chloride,
Using vinyl bromide, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, butyl maleate, octyl maleate, butyl fumarate , octyl fumarate, glycidyl acrylate, glycidyl methacrylate, droxyethyl methacrylate, -hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, ethylene glycol dimethacrylate Using acid ester, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, and as unsaturated carboxylic acid amide, acrylamide, methacrylamide, methylol acrylamide,
Butoxymethylolacrylamide was used, and as the unsaturated nitrile, acrylonitrile was used, and as the unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic acid ester, fumaric acid ester, Using itaconic acid acid ester,
Also, as acrylic compounds, allyl acetate, allyl glycidyl ether, allyl methacrylate, allyl acrylate,
Diallyl itaconate was used, vinyl, lysine, and vinyl imitasol were used as nitrogen-containing compounds, and ethylene, propylene, hexene, octene, and hydrocarbons were used.
Styrene, vinyltoluene, and butadiene are used, and as vinylsilane compounds, dimethylvinylmethoxysilane, dimethylethylethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, γ-methacryloxybrobyltrimethoxysilane, γ-methacryloxypropyl This method uses methyldimethoxysilane.

The polyester resin aqueous dispersion, modified polyester resin aqueous dispersion, and mixture thereof obtained in this manner contain crosslinking agents such as epoxy resin, melamine resin, phenol resin, and isocyanate, acrylic resin emulsion, urethane resin emulsion, and silane coupling. surfactants and viscosity modifiers to improve wettability, colorants, fillers such as inorganic or organic particles, anti-blocking agents, antistatic agents, etc.
Ultraviolet absorbers and the like may be added to an extent that does not impair the required performance.

〔Effect of the invention 〕

Since the aqueous dispersion of the present invention obtained in this manner is completely water-based, there is no risk of fire, and by pre-treating polypropylene films and molded bodies, it can be used as a barrier coating agent, heat sealing agent, or cellophane ink. The adhesion of printing inks such as , U■ ink is improved.

Furthermore, since the surface of the film is non-adhesive, the film can be wound up and can be used in both in-line and outline processes, improving the productivity of polypropylene films.

〔Example 〕

Hereinafter, the present invention will be specifically explained using Examples.

Example 1 As acid components, 30 mol% of terephthalic acid, 30 mol% of isophthalic acid, 32.5 mol% of adipic acid, 75 mol% of 5-sodium sulfoisophthalic acid, 42 mol% of ethylene glycol as diol components,
A polycondensation reaction was carried out using 58 mol % of neopentyl glycol by a known method to obtain a polyester resin having a molecule J of 110,000 and a glass transition point of 15°C. This was dispersed and dissolved in water at 80°C to obtain an aqueous dispersion with a solid content of 30% by weight.

Next, this aqueous dispersion was diluted to a solid content of 10 double stars, and further mixed with 1% silica and a wax emulsion (N, 20% V).
A coating agent was prepared by blending 1%.

This coating agent was applied to a biaxially oriented polypropylene film (hereinafter referred to as O
After applying the film to a solid film thickness of 1 μm on a PP film (hereinafter referred to as PP film), it was dried at 100° C. for 5 minutes to obtain a processed OPP film (I).

Example 2 Polyester resin water dispersion Kubes Resin A-810, T
g 45°C sodium sulfonate type resin, solid content 30% by weight, Takamatsu Yushi Co., Ltd.) 533 parts by weight, benzoyl peroxide 2 parts by weight, Blysurf A-215C (Daiichi Kogyo Seiyaku Co., Ltd.) 3 .5 parts by weight, methyl methacrylate 15
Parts by weight and 321.5 parts by weight of ion-exchanged water were charged into a four-bottle flask equipped with a cooling tube, nitrogen gas was blown into the flask while stirring to sufficiently deoxidize, and then the temperature was raised.

When the liquid temperature reaches 70°C, add methyl methacrylate 1
A mixed solution of 0.5ffiJt parts and 20 parts by weight of glycidyl methacrylate is added dropwise over 40 to 50 minutes under control at 75 to 80°C.

After the completion of dropping, maintain the liquid temperature at 80-85°C for 180 minutes.
Terminate the reaction. The mixture was cooled to below 25°C with stirring to obtain a stable aqueous dispersion with a solid content of 30% by weight and a pH of 4.2.

As in Example 1, this was diluted to a solid content of 10%, and silica and wax emulsion were mixed to prepare a coating liquid.
○Processed into PP film and processed oPP film (II)
I got it.

Example 3 Polyester resin water dispersion (Bess Resin A210.7g
35°C ammonium carboxylate type polyester resin,
Solid content 30% by weight, 500 parts by weight (manufactured by Takamatsu Yushi Co., Ltd.),
2 parts by weight of benzoyl peroxide, Blysurf A-217
Example 2 A mixed solution of 3.5 parts by weight of E (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 15 parts by weight of methyl methacrylate, 344.5 parts by weight of ion-exchanged water, 115 parts by weight of methyl methacrylate, and 20 parts by weight of glycidyl methacrylate was prepared. The reaction proceeded in the same manner as above to obtain a stable aqueous dispersion with a solid content of 30% by weight and a pH of 7.0.

This was mixed with silica and wax emulsion in the same manner as in Example 2, and then processed into a QPP film to obtain a processed OPP film (III).

Comparative example 1 Untreated OPP film Comparative example 2 Commercially available corona discharge treated PP film Comparative example 3 An acrylic copolymer emulsion (Movinyl 760; manufactured by Hoechst Synthesis Co., Ltd.) was applied to an untreated PP film with a solid film thickness of 1 μm. A processed PP film (1'V) was obtained by processing in the same manner as in the example.

As described above, vinylidene chloride latex (Kurehalon Ao; manufactured by Kureha Chemical Co., Ltd.) and cellophane ink (manufactured by Toyo Ink Co., Ltd., CC3T62 white) were applied to the six types of OPP films to a solid film thickness of 2 μm. It was dried at 95°C for 5 minutes and subjected to an adhesion test and a blocking test.

Similarly, UV ink (Morohoshi Ink Co., Ltd., UV Shine Beni T) was applied, and an ultra-high pressure mercury lamp was irradiated for 5 minutes to perform an adhesion test and a blocking test.

Adhesion Test A cellophane tape (manufactured by Chiban Co., Ltd.) was attached to the processing agent-coated surface of each of the PP films obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and the cellophane tape was smoothed with a rubber roller to make it adhere. The adhesion between the film and the coating material was determined by 180° peeling.

Blowing test The processing agent-coated side and back side (unprocessed side) of each OPP film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were superimposed, and 50%
After applying a load of 0 g/am2 and leaving it for 24 hours in an R895% atmosphere, the two stacked films were peeled off and the blocking property was evaluated.

The results of these tests are shown in the table below.

Adhesion 0; Δ completely remained on the OPP film; Partially transferred to the cellophane tape side ×; Most transferred to the cellophane tape side Blocking O1 The two films can be peeled off without any resistance.

x: Blocking was present.As shown in the figure, it was revealed that the OPP films of Examples 1 to 3 had good adhesion and no stickiness.

Claims (1)

[Claims] Polyethylene oxide, carboxyl group,
Polyester resin aqueous dispersion with a molecular weight of 2000 to 30000 containing water-soluble components such as carbonyl groups, amino groups, methylcarbonyl groups, carboxylates, sulfonates, sulfate ester salts, phosphate ester salts, and quaternary ammonium salts ( An anchor coating agent for polypropylene whose main component is an aqueous dispersion (B) in which A) and/or (A) is modified by using 1 to 300% by weight of a polyester resin with a compound having a polymerizable double bond.