JPH01234451A - Aqueous resin dispersion - Google Patents

Abstract

PURPOSE:To obtain a resin aqueous dispersion which is suitable for a coating agent, because of its excellent low-temperature adhesion to untreated polypropylene, by dispersing resin particles comprising a specific chlorinated polypropylene and a specific ethylene copolymer in water using a water-soluble acrylic resin. CONSTITUTION:(A) 100 pts.wt. of resin particles comprising A1: a chlorinated polypropylene having less than 0.1 poise viscosity and 15-40wt.% chlorine content, A2: an ethylene copolymer prepared by copolymerization of 50-95wt.% of ethylene and at least one of maleic anhydride and acrylic lower alkyl esters, having 1-30g/10min. melt flow index at a weight ratio of 1/1-1/30 are dispersed in water using (B) 2-20 pts.wt. of a water-soluble (meth)acrylic resin, which is a neutralization product of an acrylic copolymer from monomers of formula I and/or formula II (R1 is H; R2 is 1-4C alkyl; R3, R4 are H; A is O or the like) and formula III (R5 is 1-22C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aqueous resin dispersion useful as a polypropylene film, an aqueous heat sealing agent for polypropylene molded products, or an aqueous anchor coating agent.

This aqueous dispersion can be used as an aqueous heat-sealing agent for polypropylene films used to shape bags for snacks, seaweed, and frozen desserts, as well as as an adhesive for hot stamping polypropylene molded products, automobile parts for polypropylene molded products, home appliance parts, etc.
Anchor coating agent (primer) for painting daily goods,
It is useful as an adhesive for polypropylene fibers and nonwoven fabrics, and as a heat sealing agent for polypropylene kesa containers and lids.

[Prior art]

Chlorinated polypropylene with a chlorine content of 20 to 40% has good adhesion to polypropylene, so it can be used as a thermal adhesive (heat sealing agent) for biaxially oriented polypropylene films with excellent transparency and strength. Used as a primer, paint, and ink binder for molded products. However, because the difference between the thermal decomposition temperature (approximately 150°C) and the melting temperature (85 to 105°C) is small, chlorinated polypropylene is not used in a hot melt state, but instead is dissolved in an organic solvent such as toluene. The reality is that it is used.

In addition, in order to improve the adhesion between polypropylene films and other substrates, or to improve the cold resistance, impact resistance, slip properties, pigment compatibility, etc. of polypropylene, ethylene-vinyl acetate valves are added to chlorinated polypropylene. A molded body, resins such as linear polyester, thermoplastic polyurethane, and thermoplastic (meth)acrylic resin, and slip agents such as fatty acid amide, polyone fin wax fine powder, and inorganic fine powder are added and dissolved in a solvent. used.

[Problem to be solved by the invention] Since these are used as organic solvent-based coating agents, they pose problems in the working environment, fire safety, and residual solvent after coating. There are high expectations for the development of mold adhesives.

Considering the working environment issues and fire safety issues associated with this solution, we first created a substantially safe and non-polluting aqueous dispersion of chlorinated polypropylene containing water by replacing organic solvents such as toluene with water. vi'm and proposed it as a low-temperature heat sealing agent for polypropylene films (t￥j Kaisho 5
8-120655).

However, although the aqueous dispersion of the invention can adhere at low temperatures to polypropylene that has been subjected to surface oxidation treatments such as corona treatment and flame treatment, it cannot adhere to polypropylene that has not undergone any treatment at low temperatures (110 ℃ or below), there is almost no adhesion, and the thermal adhesion temperature must be set near the melting point of polypropylene, that is, near the thermal decomposition temperature of chlorinated polypropylene, and the application is limited to oxidized polypropylene. In addition, when producing an aqueous dispersion, ordinary chlorinated polypropylene has a high melt viscosity because it is made from polypropylene with a molecular weight of 20,000 or more, and the average particle size of the resulting aqueous dispersion becomes coarse. Static stability is improved by reducing the average particle size in the aqueous dispersion obtained by using a thermoplastic resin with a low viscosity, that is, a large melt flow ratio, or a wax. It was actually ft. As a result, the cohesive strength of the dried film obtained from the aqueous dispersion was poor, making it unsuitable for applications requiring a high level of adhesive strength.

The object of the present invention is to provide a substantially non-polluting and safe aqueous dispersion which overcomes the above-mentioned disadvantages and provides a coating with excellent low temperature adhesion to non-oxidized polypropylene films and molded articles.

[Means for solving the problem] Unexploded 8A has a viscosity of 0.1 poise or less when measured in a toluene solution at 25°C, 10 pages low solids content, and has a chlorine content of 15 to 405 to 40 parts by weight hydrogenated polypropylene B), ethylene content 50 to 950 to 95 parts by weight The copolymerization component is typically at least one of maleic anhydride, lower alkyl acrylate, lower alkyl methacrylate, and vinyl acetate. It is an ethylene thread valve type body with a sweetness and temperature of 190℃ measured according to JIS-6760.
, the melt flow ratio in the 2.16 kp load trap is 1.
~30g/10 minutes Water-soluble (meth) resin particles in which 100 parts by weight of the resin particles have an amino group, in which the above components A) and B) are distributed in a weight ratio of 1/1 to 1/30, and the sweetness is 9. An aqueous resin dispersion prepared by dispersing 2 to 20 parts by weight of an acrylic resin in water is provided.

Chlorinated polypropylene is made by converting polypropylene to toluene,
Mt containing chlorine can be obtained by dissolving it in a solvent such as heptane or contacting it in an undissolved state with chlorine gas.
It is known that only polypropylene with a weight of 40% by weight or less will adhere to polypropylene. However, when used in a molten state, chlorinated polypropylene, which has a high chlorine content, has poor thermal stability and is easily dehydrochlorinated. Used as a solvent-based adhesive.

The present inventors believe that this poor thermal stability is due to the fact that chlorinated polypropylene has a low thermal decomposition temperature (approximately 150°C) and is difficult to melt. They proposed dispersing it in water by melt-mixing it in a short time by using it in combination with a resin with good compatibility and a low softening temperature, such as N@ body (Japanese Patent Application Laid-open No. 120655/1982). However, as previously mentioned, polypropylene that has undergone surface treatments such as corona treatment or flame treatment has a practical optical contact strength at temperatures below the melting point of chlorinated polypropylene, but polypropylene that has not been subjected to any oxidation treatment Untreated polypropylene showed little or very weak adhesion at temperatures below the melting point of polypropylene.

The reason for this is that ordinary chlorinated polypropylene resin is made from polypropylene, which has a molecular weight of 20,000 or more and has a high melt viscosity. Therefore, even if a resin with a low softening temperature and good compatibility is used, such as an ethylene/vinyl acetate valve type body, the thermal decomposition temperature and softening temperature of the chlorinated polypropylene will be too high when mixed during melting. Because the difference is only a teaspoon, it is necessary to melt and mix in a short time at a low temperature, and the dispersion of the chlorinated polypropylene into the ethylene-vinyl acetate valve-shaped body is not completely compatible, and the chlorinated polypropylene Because the island, ethylene/vinyl acetate valve-shaped body is an unrestricted structure of the sea island that has become the sea, the original performance of chlorinated polypropylene, which is the property of polypropylene, is not expressed, and the ethylene Φ acetate This is thought to be due to the fact that it acts as a cohesive ash to improve the adhesion of vinyl co-NfF and (meth)acrylic resins having amino groups to the treated surface of polypropylene.

Therefore, in order to exhibit the original properties of chlorinated polypropylene, it is believed that it is necessary to have a form in which it is uniformly dispersed in the sea, as when it is dissolved in an organic solvent.

Based on this reasoning, the present inventors believe that if it is possible to make the melting of chlorinated polypropylene easier and lower its viscosity by widening the difference between the thermal decomposition temperature and the softening temperature of chlorinated polypropylene, Because more uniform dispersion is possible
I thought about whether or not it was possible, and did a lot of research.

That is, in order to reduce the total viscosity of chlorinated polypropylene when it is melted, use of chlorinated polypropylene with a low molecular weight, use of chlorinated polypropylene made from amorphous polypropylene, and intermolecular cohesive force'! ! - In order to lower the noise level, I thought that using chlorinated polypropylene modified with hydroxy methacrylate would be a good idea, which led me to complete the present invention.

Among the chlorinated polypropylenes of component A) of the present invention, those that have a large difference between the thermal decomposition temperature and the softening temperature and can be bonded to non-oxidized polypropylene are prepared in a toluene solution at 25°C and a solids concentration of 10% by weight. The chlorinated polypropylene has a viscosity of 0.1 poise or less when measured in the following state, and a chlorine content of 15 to 40 parts by weight. The viscosity of the solution is 0
．． If it exceeds 1 poise, the adhesion to untreated polypropylene tends to decrease. Also, the chlorine content is 15
If the weight is less than 40% by weight, low-temperature adhesion will be poor, and if it exceeds 40% by weight, the adhesion to non-oxidized polypropylene will be poor.

B) The ethylene copolymer with a TiV of 50 to 90% is used to completely improve the storage stability of the aqueous resin dispersion.
It is a copolymer of 5 weight Q% and other vinyl monomers,
190°C, measured according to JIS-6760, 2.1
6 - Melt flow ratio (MFR) under load is 1
~30 f/10 minutes.

Other at-forms include maleic anhydride, (meth)acrylic acid lower alkyl ester (the number of carbon atoms in the alkyl group is 1 to 1).
8) Vinyl acetate, acrylic acid, methacrylic acid, etc. are used.

If the ethylene content is less than 50 mm by weight, the adhesion to untreated polypropylene tends to deteriorate, probably because the compatibility with the chlorinated polypropylene that is component A) becomes poor.

A similar tendency exists even when the value exceeds 95%. Historically, the valve-shaped bottom part that has a similar electrical sweetness with ethylene contains at least one of the following: maleic anhydride, acrylic acid alkyl ester, methacrylic acid alkyl ester, and vinyl acetate, which have good compatibility with the chlorinated polypropylene component (A). It is. Examples of ethylene thread valve-type bodies co-sweetened with such monomers include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylic acid co-M8 body, ethylene-methyl acrylate valve-type body, and ethylene-vinyl acetate copolymer. -Ethyl acrylate cosalt combination, ethylene-
Binary and tertiary copolymers such as butyl acrylate valve type polymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate-maleic anhydride valve type polymer, and these acrylic acid, methacrylic acid or Examples include maleic anhydride modified products, such as maleic anhydride grafted ethylene-vinyl acetate co-N-adducts. Among these, ethylene-vinyl acetate copolymer is preferred because it has the best compatibility with chlorinated polypropylene.

The ethylene copolymer of Kohori et al. was measured in accordance with JISK-6760 at 190°C and 2.16 kI? Melt flow ratio (flFR) under load is 1 to 30 P71
It is 0 minutes. If the time exceeds 710 minutes, the cohesive force of the film obtained from the aqueous dispersion will be weak, and sufficient adhesive strength will not be obtained. It is rough and the static stability of the dispersion liquid is lost.

The weight ratio of A) the chlorinated polypropylene for IliZ and B) the two-thin V-thread copolymer for H is 171 to 1/30.

A) Even if the ratio is increased, the low-temperature adhesion of the film to non-oxidized polypropylene does not improve.

On the contrary, the adhesive strength to different materials tends to be low. If the proportion of component B) is increased beyond 1/30, not only will the low-temperature adhesion of the film to non-oxidized polypropylene deteriorate, but also the static stability of the dispersion will deteriorate.

Next, the weight ratio of component A) and component 8) is 171 to 1/30.
A water-soluble (meth)acrylic resin having an amine group, which is a dispersant used when dispersing the resin set 5z in water, will be mentioned.

A water-soluble (meth)acrylic resin having an amino group is an important component necessary for emulsifying, dispersing, and stabilizing the above-mentioned thermoplastic resin in water, and is disclosed in JP-A-58-118843. This is the general formula, and /'f is the monomer represented by 10 to 80 moles, and (b) the general formula is CH2=C11COOR.

It is a neutralized product obtained by partially or completely neutralizing the copolymer obtained by completely copolymerizing with 90 to 20 moles of the monomer represented by [the abbreviation in the formula is Same as above].

The above component (a) includes N,N-dimethylamine ethyl (meth)acrylate, N,N-dimethylaminoethyl (
Examples include meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylamine-2-hydroxypropyl(meth)acrylate, 4-vinylpyridine, and 2-vinylpyridine.

(b) 5y: acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, Stearyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, base/(meth)acrylate
Alkyl of acrylic acid or methacrylic acid, such as zyl,
Alkenyl, cycloalkyl, and aralkyl esters are included. These may be used alone or in combination
More than one species can be combined and used.

In addition to the monomers of components (a) and (b), polymerizable polymers such as vinyl acetate, styrene, vinyl ether, etc. are used, if necessary.

The component (b) is the molar fraction of the acrylic ester i of the component (i) in the copolymer component, 'fi=Mi, and the carbon tl k N of the acrylic ester i.
If i is the total sum of the product of Ml and Nl (ΣMi N
It is preferable to select and use component (A) in such a way that i) has a value of o, s, preferably a value of 1 to 8.

If ΣMiNi is less than 0.5, the lipophilicity of the neutralized copolymer will be weak, and if it exceeds 10, the lipophilicity will be strong, making it impossible to produce a stable aqueous dispersion in either case.

The M bendable mass bodies such as (a) component and (b) component are as follows: (
Iso component 10 to 80 mol%, preferably 15 to 75 mol%, (b) component 90 to 20 mol%, preferably 85 to 2 mol%
0 to 180°C in the presence of a heavy initiator with a 5 molar ratio
, preferably at 40 to 120°C for 0.5 to 20 hours, preferably 2 to 10 hours, to produce a copolymer. This weighting reaction is preferably carried out in the presence of water or a hydrophilic solvent such as ethyl alcohol, inglobil alcohol or cellosolve.

As a superposition initiator, azobisin butyronitrile, (-
Butyl peroxyisobutyrate, 1,1-bis(t-
Examples include butylperoxy)cyclohexene, butylperoxybenzoate, and the like.

(a) If the component snow is less than 10 moles, the hydrophilicity of the neutralized copolymer obtained is weak, and if it exceeds 80 moles, the hydrophilicity of the neutralized product becomes strong, resulting in a stable aqueous dispersion. cannot be manufactured. (b) If the mole value of the component is less than 20, the lipophilicity of the neutralized copolymer obtained will be weak, and
If the molar ratio is exceeded, the lipophilicity of the middle-aged product is too strong, and in any case, a stable aqueous dispersion cannot be obtained.

Acids for neutralizing this co-TL sweetener include formic acid, acetic acid, hydrochloric acid, phosphoric acid, nitric acid, etc. Among these, formic acid, acetic acid, and hydrochloric acid, which are volatile at room temperature, were used. When the aqueous dispersion dries to form a film, these acids are liberated from the neutralized product and the hydrophobicity of the dispersant increases, resulting in good water resistance of the film.

In the neutralization reaction, the copolymer and acid are mixed at 20 to 100°C at a temperature of 0.1 to
It is removed by reacting for 3 hours.

In addition, before the production of the copolymer, (a) FM and 100% are neutralized in advance with these acids, and this and (2) the neck of FM and the like are brought together with the body to form the copolymer. A neutralized product may also be produced.The amount of acid used for neutralization is 10 to 100 moles of component (a) constituting the copolymer.

Moreover, the manufacturing method of the aqueous dispersion is, for example! +￥￥Sho 5
8-120655, the V thermoplastic resin is completely continuously fed into the hopper of a co-directional mesh type twin screw extruder. The aqueous solution of the above-mentioned water-soluble (meth)acrylic resin having amino groups is completely continuously supplied and melted and kneaded, and then water is continuously supplied from the second vent and extruded from the tie into the water tube. In particular, it can be manufactured.

[Effect]

Although the aqueous resin dispersion obtained by the present invention does not contain organic solvents such as toluene, it does not have low-temperature adhesion to untreated polypropylene, which is a drawback of conventional aqueous dispersions. It is useful as a coating agent with excellent work environment and hygiene.

〔Example" The present invention will be specifically explained below using examples.

(Reference Example-1) (Chlorinated polypropylene) A toluene solution of Toyo Kasei's chlorinated polypropylene (JPP) was solidified by removing the toluene from the solvent at 70°C in a vacuum dryer for 24 hours. An index with .

Table-1 Reference Example-2> Production example of water-soluble (meth)acrylic resin with amino group N, N-dimethylamine ethyl methacrylate 62.9
parts, butyl methacrylate 71 parts, lauryl methacrylate 25-4 m2 and Improvil alcohol 200 parts
The reactor was charged with a reactor equipped with a stirrer, a reflux condenser, a temperature gauge, and an inlet, and after purging with nitrogen gas, 0.9 part of 2,2'-azobisisobutyrotrile was added as a sweet initiator. , an overlapping reaction was performed at 80° C. for 4 hours. Next, after neutralizing with 24 parts of acetic acid, water was added while inglobil alcohol was distilled off, to finally obtain a viscous aqueous dispersant solution with a solid content of 35%.

Examples 1 to 3, Comparative Examples 1 to 2 Sample ClPP-6 in Table 1 and ethylene-vinyl acetate co-N composite [Mitsubishi Polyethylene EVA V manufactured by Mitsubishi Yuka Co., Ltd.
-601S” (part name), MFR: 15?710 minutes,
A street oil composition containing vinyl acetate-containing fir 28 weight t%] distributed at the M weight ratio shown in Table 2 at 100 weight weight/hour;! 11 attached, co-rotating interlocking type twin screw extrusion screw (manufactured by Ikezuki Tekko Co., Ltd., product name PCyr-4s, triple thread shallow groove type, L/D=
30) was continuously supplied from the hopper. In addition, from the supply port provided in the pent part of the same extruder, the aqueous dispersant solution formed in Reference Example 2 is continuously supplied under pressure with a gear pump at a ratio of 3 (is/hour). Continuously supply hot water at 70°C at a rate of 80 parts/hour using a Ginger bong from the supply port provided in the vent section, under the conditions of extrusion temperature of 130°C and screw rotation speed of 300 revolutions/min. Upon extrusion, a milky white aqueous resin dispersion was obtained.

The aqueous resin dispersion of Kohori et al. was evaluated according to the method of the authors. The results are shown in Table-2.

a): Stability of the aqueous resin dispersion The resulting aqueous dispersion was adjusted to have a total solid content of 451%, and the resulting aqueous dispersion was sealed in a graduated cylinder and stored at room temperature for one month. For the upper layer b, those where the resin layer floated or sedimented and separated at the bottom were evaluated as poor, and those with no separation were evaluated as good.

b); Low-temperature ff1l biaxially oriented polypropylene film on untreated polypropylene
500'' (Product name) Untreated type, 40 μJ thick, coated with a bar coater so that the film thickness after drying is 5 μ.
It was dried for 10 seconds with a hot air dryer at 110° C. to form a film, thereby obtaining a film with an adhesive film.

The coated surfaces (coating surfaces) of the fallen films with reciprocal films were placed on top of each other, and heated at 90°C using a hot plate type heat sealer at a pressure of 2 kg/ctA s and a time of 0.5 seconds.
Heat sealed under temperature conditions of 110℃ and 150℃, 15
Cut it into a simple width strip.

This sample was pulled at a tensile speed of 300t using a tensile tester.
T beer test based on component speed? This is implementation 1-. (Enter the maximum value) C): Adhesion between untreated polypropylene and different materials Resin aqueous dispersion obtained? It was coated on the following various substrates using a bar coater so that the film thickness after drying was 5 μm, and dried for 10 seconds with a hot air dryer at 110° C. to release the 5 μm film to obtain an adhesive film. The surface of this adhesive film was layered with a non-gold-treated poly-10-pyrene sheet (Noblen MA-61 (part name) manufactured by Mitsubishi Yuka ■) (thickness 0.3 m), and was heated to 2 kg/d at 150°C. It was heat-sealed under conditions of 15 seconds and cut into strips with a width of 15 mm.

This sample was subjected to a 180'' beer test using a tensile tester at a tensile speed of 300+m/min. (Maximum value is listed) 1) Biaxially stretched polyester film; (P E '1
) Abbreviated as Toyobo 1 Varnishpet 'l'4100' Thickness 16μ 2) Biaxially oriented polyamide film: <PA,>
Toyo IT! “Harden Film N 1100” Thickness 2
5. ff 3) Polycarbonate film: (PC), handmade by Mitsubishi Gas Chemical.

Thickness 50μ 4) Polystyrene biaxially stretched film: Abbreviated as <ops> Mitsubishi Monsando Kasei “Santo Clear OPS” Thickness 150
μ 5) Aluminum foil; Abbreviated as <AA', > Tokai Metals ↓ Thickness 25μ Examples 4 to 6, Comparative Examples 3 to 7 Samples ClPP-1 to ClPP-8 in Table 1A and ethylene-methyl methacrylate MO body [Sumitomo Chemical Company ° Acrift ~ VD2ot' (nf product name); MF R1
2S' 710 minutes; Methyl methacrylate-containing glaze
The resin set that was placed in the ■ differentiation of "Z Kuchikaku" 1/9 was made into an aqueous dispersion liquid just like the previous example, and a review was made. The results are shown in Table-3.

Examples 7 to 11, Comparative Examples 8 to 11 Samples ClPP-6 in Table 1 and Table 48C show 7 m
Evaluation was carried out in the same manner except that the ethylene-vinyl acetate co-directly attached body having an index was distributed to the door at a weight ratio of 1/19. The results are shown in the same table.

Plant powder of ethylene-vinyl acetate valve-shaped body made by Nippon Sei ``Soarex Di'' Cm aa
Name) *2 Mitsubishi DuPont 'Evaflex 40' C
mh name) *3 Mitsubishi Yuka Co., Ltd.
Product name) *, s Eiy' Yubon "Evaflex 410" (1) *5 Mitsui DuPont back ° Evaflex 460" (l ) *6 Sumitomo Chemical "Sumitate L) B 10' (〃) *7 Tosoh Rip "Ultrasen VE540" (Product name) *8 Tosoh Rip "Ultrasen VE536'(# ) *9 Sumitomo Chemical Evatate D1012" (l ) (J-1 Shimokanpaku) Comparative Example 12 In Example 1 In place of the water-soluble (meth)acrylic 'J' resin used, a 35% by weight aqueous solution of partially saponified polyvinyl alcohol [Kuraray Kuraray Boval PVA420' (trade name), degree of saponification 80 mol] was used. Aqueous dispersion i was obtained under the same conditions except for the following.

The standing stability of this aqueous resin dispersion was good. In addition, as in Example 1, low temperature adhesion to untreated polypropylene was measured under heat sealing conditions of 90°C, 110°C, and 150°C (pressure 2 kg/i% time 0.5 seconds). 40f/15■, 70r/15 fight, 1109
/ 15 lII+.

Furthermore, as for the adhesion between untreated polypropylene and different materials, PET, PA, PC< o
When we measured the 180° building strength with ps and alt, they were 170? 715m, 230f715
■, 140g/15 decoration, 180g/15mm, 47
It was 0t715m.

Examples 12 to 13, Comparative Examples 13 to 15 Resin aqueous dispersions were prepared in the same manner as in Example 2, except that the ethylene-vinyl acetate copolymer used in Example 2 was replaced with the ethylene copolymer shown in Table 5. was obtained, and the fL was evaluated. The results are shown in the same table.

*11 Ethylene-acrylic acid valve-type body made by Mitsubishi Yuka Yukalon EAA A221M (M product name) Acrylic acid content 8.5 Gravimetric method MF R7f 710 minutes *12 Ethylene-methacrylic acid copolymer Mitsui Typon Iwa 1 New Krell N-0908C" (trade name) Methacrylic acid content fi9.0 heavy duty MFR8t710 minutes*13 Ethylene-ethyl acrylate-maleic anhydride copolymer Sumika CF "Bondine LX-4110" (trade name) Acrylic acid Ethyl containing t8.2 weight set, maleic anhydride containing JI0.8 weight set MFR5P710 minutes*14 Ethylene-butene valve type body Mitsui Petrochemical back "Tafmer A2009D" (part name) butene containing ft15 weight set, MF R205' 710 minutes (margin below)

Claims (1)

[Scope of Claims] A) Chlorination having a viscosity of 0.1 poise or less as measured in a toluene solution with a solid content of 10% by weight at 25°C and a chlorine content of 15 to 40% by weight. polypropylene. B), an ethylene copolymer having an ethylene content of 50 to 95% by weight and copolymerized with at least one of maleic anhydride, lower alkyl acrylate, lower alkyl methacrylate, and vinyl acetate as other copolymer components; Polymer, 190°C measured according to JIS-K6760
, the melt flow ratio at 2.16 kg load is 1
~30 g/10 minutes Water-soluble (meth)acrylic resin particles in which 100 parts by weight of resin particles containing the above A) and B) components in a weight ratio of 1/1 to 1/30 have amino groups. An aqueous resin dispersion prepared by dispersing 2 to 20 parts by weight of resin in water. C) A water-soluble (meth)acrylic resin with an amino group is a unit represented by the general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A copolymer of 10 to 80 mol% of a monomer and 90 to 20 mol% of a monomer represented by (b), general formula, ▲mathematical formula, chemical formula, table, etc. is partially or completely treated with an acid. A resin aqueous dispersion characterized by being a neutralized product of an acrylic copolymer having a neutralized structure [wherein R_1 is H or CH_3; R_2 is a carbon number of 1
~4 alkylene group or hydroxy-substituted alkylene group; R_3 and R_4 are H or an alkyl group having 1 to 4 carbon atoms; R_5 is an alkyl group, alkenyl group, cycloalkyl group, or benzyl group having 1 to 22 carbon atoms; A is O or N
H].