JPH01245041A - Aqueous resin composition - Google Patents

Abstract

PURPOSE:To obtain an aqueous resin composition, containing an alkenylbenzene based polymer and chlorinated polyolefin, capable of exhibiting excellent adhesiveness to polyolefin based substrates without pretreatment with primers, etc., and useful as coatings or adhesives. CONSTITUTION:An aqueous resin composition, containing (A) 100pts.wt. alkenylbenzene based polymer containing 50-100wt.%, preferably 50-95wt.% alkenylbenzene with (B) 1-100pts.wt., preferably 2-60pts.wt. chlorinated polyolefin having 20-45wt.% chlorination degree and produced by slowly adding the component (B) which is dissolved in a solvent or thermally melted into an aqueous medium containing the component (A) dispersed therein or dissolving the component (B) in a monomer of the component (A) in polymerization thereof or dissolving the component (B) in a solvent and then mixing the resultant solution with the monomer and polymerizing the obtained mixture in a state dispersed in the aqueous medium.

Description

Detailed Description of the Invention (a) Object of the Invention [Field of Industrial Application] The present invention relates to an aqueous #oil composition, and more specifically, the present invention relates to a water-based #fat composition, and more specifically, to a polyolefin base material, the polyolefin base material is subjected to pretreatment or primer treatment. The present invention relates to an aqueous resin composition that is useful as a coating agent or adhesive that has good adhesion without causing any damage.

[Conventional technology]

As is well known, polyolefin base materials such as propylene resins and ethylene/propylene resins have outstanding properties in terms of weather resistance, aging resistance, ozone resistance, heat resistance, etc. In addition, it has excellent moldability, so its potential and future potential as a new material has been highly evaluated, and in recent years it has been produced in large quantities industrially, and the development of a wide range of applications has been actively promoted. It is expected that there will be a huge need for it, and it is already being put into practical use as a material for the automobile industry and parts for home appliances, for example.

However, since these polyolefin base materials do not have polar groups in their molecules, and are so-called non-polar and chemically extremely inactive polymeric substances, their solubility in solvents is also extremely low.

This characteristic can be said to be extremely favorable depending on the application and usage conditions, but for application fields that require painting or adhesion, it poses a problem that is truly troublesome and difficult to solve technically.

In other words, it is extremely difficult to completely paint or adhere other parts to molded parts and products made of non-polar polymeric materials as desired. However, there are frequent cases where the coating film peels off in a short period of time, and the desired cosmetic and protective purposes cannot be achieved.

As a means to prevent such inconveniences, products made from this type of polymer material have conventionally been treated with ultraviolet or electron beam irradiation, corona discharge, plasma contact, or oxidation treatment with ozone gas before painting. Alternatively, surface (base) treatment methods including chemical treatment by immersion in a mixed solution of concentrated sulfuric acid, organic monocarboxylic acid, and phosphoric acid, etc. are recommended and have been practiced for quite some time. However, with these methods, depending on the shape of the target product, it may be difficult to apply uniform treatment to the entire surface, and the degree of activation of the surface obtained by treatment may not necessarily be sufficient. This method has drawbacks such as not forming a film in many cases, and in addition, requiring various expensive equipment to carry out specific surface treatments, resulting in an economical disadvantage.

On the other hand, research has been actively conducted to improve and develop surface treatment methods by applying primers as a more advantageous and effective alternative to these methods, and as a result, various primer compositions have been invented and proposed. (For example, JP-A-61-
No. 192743, JP-A-61-78844, JP-A-6
2-190209)) has been put into practical use.

Methods using these primers also require primer application and drying steps, and are inevitably inferior in terms of economy and workability compared to the 1-coat-1-finish method. In addition, JP-A-61-231069, JP-A-60
No.-38436 is provided. However, like the primers mentioned above, these compositions are all solvent-based,
The results were unsatisfactory in terms of fire risk, hazardous working environment, and economic efficiency.

[Problem to be solved by the invention]

As mentioned above, in order to apply paints and adhesives to polyolefins, pretreatment to activate the surface of polyolefins,
Alternatively, a solvent-based primer was required, but the present invention can be applied to polyolefins without any of the various pretreatments or primers described above.

The objective is to provide a water-based resin composition that exhibits excellent adhesion and is useful as a paint or adhesive, and furthermore, simplifies the process, is economical, is toxic, harmful, and poses a risk of fire. It is an object of the present invention to provide an aqueous resin composition that is more useful to industry.

(B) Structure of the invention [Means for solving the problem] As a result of intensive research and consideration regarding the above problem, the present inventors have found that chlorinated polyolefin is forced into an aqueous medium in which an alkenylbenzene polymer is dispersed. By dispersing or polymerizing alkenylbenyne etc. in an aqueous medium in the coexistence of a chlorinated polyolefin to form an alkenylbenzene polymer, an aqueous polymer with good adhesion to polyolefin and excellent storage stability can be obtained. It was discovered that a resin composition can be obtained, and the present invention was completed.

That is, 1 the present invention uses chlorine having a chlorination degree of 20 to 45% by weight based on 100 parts by weight of an alkenylbenzene polymer in which 50% by weight or more of the monomers constituting the polymer are alkenylbenzene. The present invention relates to an aqueous resin composition containing 1 to 100 parts by weight of polyolefin.

Here, the alkenylbenzene polymer (A) is a polymer of alkenylbenzene or a copolymer component thereof, and alkenylbenyne accounts for 50% by weight or more of the total weight.

The chlorinated polyolefin (B) is an olefin with a degree of chlorination of 20 to 45 percent by weight.The present invention will be explained in more detail below.

<Alkenylbenzene polymer (A)> (1) Composition of alkenylbenzene polymer The base alkenylbenzene polymer used in the present invention contains alkenyl as a polymerizable Q1 polymer in its resin. 50~ benzene
100% by weight (hereinafter simply referred to as %), preferably 50 to
It contains 95% and is obtained by emulsion polymerization using general surfactants or water-soluble polymers as emulsifiers, and the degree of polymerization generally shows a wide distribution and the molecular weight is 10,000 or more. .

In addition to alkenylbenzene, one or more types of other polymerizable monopods that can be copolymerized with alkenylbenzene may be copolymerized in the E resin.

If the proportion of alkenylbenzene in the alkenylbenzene polymer is less than 50%, the reason is unclear, but
Sufficient adhesion cannot be achieved when chlorinated polyolefin is blended.

The alkenylbenzene used in the alkenylbenzene polymer used in the present invention has the following structural formula, where R1, R2, R1, and R4 represent hydrogen or a methyl group.

1 For example, styrene, vinyl 1-
Examples include toluene and α-methylstyrene.

In addition, other polymerizable I that can be copolymerized with the alkenylbenzene
The ll and h forms include methyl methacrylate, ethyl acrylate, n-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate.

1so-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, 1so-butyl vinyl ether, n-butyl vinyl ether, acrylonitrile, methacrylonitrile, vinyl acetate , vinyl chloride, vinylidene chloride, vinyl fluoride.

vinylidene fluoride, ethylene, propylene, isoprene,
Examples include chloroprene and butadiene.

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

The required physical properties of the coating film can be obtained.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, atrobic acid, citraconic acid, crotonic acid, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, allyl alcohol, acrylic amide, methacrylamide,
By using functional monomers such as diacetin acrylamide, vinyl pyrrolidone, vinyl pyridine, vinyl carbazole, glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether, crosslinking with melamine, isocyanate, polyamide, etc., or further diacetyl The physical properties of the film can also be modified by internal crosslinking using a polyvinyl single cell such as vinylbenzene, diallyl phthalate, or tetraallyloxyethane.

(2) Method for producing alkenylbenzene polymers Emulsion polymerization using ordinary emulsifiers is generally used to produce alkenylbenzene polymers.
The polymerization is not limited to this only, but polymerization can also be carried out by special methods such as a method in which a polymer substance is used as a colloid, a catalyst fragmentation method using a persulfate, and the like. Polymer substances for producing protective colloids include water-dispersible or water-soluble acrylic resins, polyester resins, urethane resins, styrene/maleic acid resins, etc. Persulfates include ammonium, potassium, and sodium salts. is generally available.

Chlorinated polyolefin (B)> The chlorinated polyolefin used in the present invention has a degree of chlorination of 20 to 45%, and among these, preferred are those that are generally said to be easy to adhere to polyolefins. . Examples of the polyolefin used in the chlorinated polyolefin include one or more copolymers of polyethylene, polypropylene, polybutylene, polyisoprene, etc., or copolymers of these with acrylic acid, vinyl acetate, vinyl chloride, etc. The degree of polymerization of chlorinated polyolefin is estimated to be several thousand to several tens of degrees. These are generally in the form of a solution using an aromatic hydrocarbon as a solvent, and the solids content thereof is generally in the range of 20 to 60%. There is also a special grade in solid form, but in this case, it is preferable to use it by dissolving it in a solvent in the present invention.

Examples of commercially available chlorinated polyolefins that can be used in the present invention are Birdren 13L (26) and 13LLB (26
), PA-15 (30), 15L (30).

15LLB (30), 14LLB (27), 17L (3
5), 17LLB (35), 35A (35), 35-A
L (35) (manufactured by Toyo Kasei Kogyo Co., Ltd.), Super Chron 773H (32), 804M (34).

803H (32), 803MW[29,5], 803L
(26), 814H (43), B (27).

EC29,5), 822(24,5), 832(27)
(manufactured by Yamaba Kokusaku Pulp Co., Ltd.), etc. In addition, in the above, the numerical value in [ ] shows the degree of chlorination of each chlorinated polyolefin.

Further, as compositions containing chlorinated polyolefins having a degree of chlorination of 20 to 45%, various commercially available products such as Superchlor
S-180 (mixture of chlorinated polyolefin with a chlorination degree of 30% and acrylic resin in a solid content ratio of 70:30; manufactured by Sanyo Kokusaku Pulp Co., Ltd.), PP primer 822 liquid (Super Chron 822 (chlorination degree A mixture of 96 parts by weight (hereinafter simply referred to as parts) of 24.5% chlorinated polyolefin and 4 parts of epoxy resin, etc.; manufactured by Yamaba Kokusaku Pulp Co., Ltd.)
, Aron 5P-1350 (solid content weight ratio of chlorinated polyolefin with chlorination degree of 35% and acrylic resin 50)
: 50 mixture; manufactured by Toagosei Kagaku Kogyo Co., Ltd.) etc. can also be used.

The amount of chlorinated polyolefin used is such that the solid content weight ratio of the alkenylbenzene polymer to the chlorinated polyolefin (in the case of a chlorinated polyolefin-containing composition, as the chlorinated polyolefin in the composition) is (A) 100 parts. (B) is used in an amount of 1 to 100 parts. These may be used alone or in combination of two or more. More preferably, by adding 2 to 60 parts, strong adhesion can be obtained. If the amount of chlorinated polyolefin is less than 1 part, the adhesion will be poor;
If the amount exceeds 0.00 parts, the adhesion will not improve much and it is not economically preferable, and if it is dissolved in a solvent and added, it becomes solvent rich, which is not preferable from the viewpoint of fire danger and toxicity.

<Method for producing an aqueous resin composition> The aqueous resin composition of the present invention is prepared by dissolving a chlorinated polyolefin (B) in a solvent or thermally melting the alkenylbenzene polymer (A) in an aqueous medium in which the alkenylbenzene polymer (A) is dispersed. It is produced by gradually adding chlorinated polyolefin (B) while stirring.

The solvent for dissolving the chlorinated polyolefin (B) may be any solvent as long as it dissolves the chlorinated polyolefin (B). Usually, such solvents include aromatic solvents such as toluene and xylene, and fats such as cyclohexane, methylcyclohexane, and ethylcyclohexane. Cyclic solvents, halogenated hydrocarbon solvents such as triclonyl ethylene, methyl chloroform, etc. are used.

In order to mix the alkenylbenzene polymer (A) and the chlorinated polyolefin (B) efficiently and stably in a short time, it is important that the viscosity of each is not too high, preferably 100%.
00 cps or less, more preferably 3000 cps or less.

In addition to the above, the aqueous resin composition of the present invention can be prepared by dissolving the chlorinated polyolefin (B) in the monomer of the alkenylbenzene polymer (A) during polymerization, or by dissolving the chlorinated polyolefin (B) in a solvent. It can also be produced by mixing with monomers and polymerizing them in a state where they are dispersed in an aqueous medium. In addition, a solvent and an emulsifier are added to chlorinated polyolefin to form a paste, which can be added as is or diluted with water to form an emulsion and added to alkenylbenzene polymers or when polymerizing alkenylbenzene polymers. However, it can be mixed efficiently.

These methods are particularly useful when it is desired to reduce the solvent content in the aqueous resin composition;
Since coagulation tends to occur, it is necessary to appropriately select polymerization conditions.

The aqueous resin composition of the present invention can also contain various pigments, fillers, thickeners, crosslinking agents such as melamine, etc.
It can be used as a binder for ink adhesives, flocking, non-woven fabrics, etc.

[Examples and comparative examples]

<Preparation of alkenylbenzene polymer (A)> (1),
Alkenylbenzene polymer (A-1) 60 parts of water was charged into a reactor equipped with a stirrer and a cooler, and the temperature inside the reactor was 85°C.
55 parts of styrene, 10 parts of methyl methacrylate, 33 parts of butyl acrylate, 2 parts of acrylic acid, 6 parts of Lebenol WZ (manufactured by Kao Soap) as an emulsifier, and 0.5 parts of potassium persulfate as a polymerization catalyst were added in water. The liquid dispersed in
It dripped over time. Thereafter, the temperature was maintained and the mixture was further aged for 2 hours, and then cooled to room temperature to obtain an emulsion polymerized aqueous copolymer dispersion having a non-volatile content of 50 parts and a viscosity of 80 cps.

(2) Alkenylbenzene polymer (A-2) Alkenylbenzene polymer (A-1 ) to obtain an aqueous copolymer dispersion having a non-volatile content of 50 parts and a viscosity of 100 cps.

(3), alkenylbenzene polymer (A-3) except that 40 parts of styrene, 25 parts of methyl methacrylate, 33 parts of 2-functional tylhexyl acrylate, and 2 parts of acrylic acid were used.
Perform emulsion polymerization in the same manner as alkylbenzene (A-1),
An aqueous copolymer dispersion having a nonvolatile content of 50% was obtained.

(4), Other resins (A-4) Freon A, which is a (meth)acrylic acid ester polymer emulsion, is a resin that does not contain alkenylbenzene.
-106, [solid content 43%, viscosity 700 cps (manufactured by Toagosei Chemical Industry Co., Ltd.)] was used.

<Preparation of chlorinated polyolefin (B)> The following was used as the chlorinated polyolefin (hereinafter abbreviated as C1-PP).

(i) Super Chron 822 (Yamaba Kokusaku Pulp Co., Ltd.)
(II) Super Chron 804M (Yamaba Kokusaku Pulp Co., Ltd.!a, degree of chlorination 24.5%, non-volatile content 30%, toluene solution) (iii) Super Chron 814H (manufactured by Yamaba Kokusaku Pulp Co., Ltd., degree of chlorination 43%, non-volatile content 60%, toluene solution) was diluted with toluene to a non-volatile content of 40% (thv) Super Chron 106H (Yamaba Kokusaku Pulp Co., Ltd.) (V) Super Chron S-180 (Yamaba Kokusaku Pulp (Yamaba Kokusaku Pulp,
Co., Ltd., solid content weight ratio 70:3 parts mixture with ct-pp Niacrylic resin, non-volatile content 40% toluene solution) (vi) Super Chron 822 45 parts Epicoat 828 (epoxy resin of Shell Petrochemical Co., Ltd.) )1
1 part curing agent was blended.

(vii) Aron S-1350 (manufactured by Toagosei Kagaku Kogyo Co., Ltd., a mixture of C1-PP with a degree of chlorination of 35% and an acrylic resin in a solid weight ratio of 50:50, a toluene solution with a non-volatile content of 40%) Example 1-13 Alkenylbenzene polymer prepared above (A-1)
or (A-2) (7) 100 parts 50 with a stirrer
A predetermined amount of the chlorinated polyolefin was gradually added dropwise to the mixture while stirring at room temperature, and stirring was continued for an additional 30 minutes after the dropwise addition was completed.

An aqueous resin composition having the formulation shown in Table 1 was obtained.

Example 14 Chlorinated polyolefin composition Aron 5P-1350 (
Toagosei Kagaku Kogyo C Co., Ltd.) 69 parts of styrene, 830 parts of 2-ethylhexyl acrylate, and 1 part of acrylic acid were used in the presence of 20 parts (2 parts as solid content) of alkenylbenzene-based polymer ( Polymerization was carried out in the same manner as in the preparation of A-1) to obtain an aqueous resin composition by emulsion polymerization with a nonvolatile content of 42.5%.

Example 15 Superchron 822 2 as chlorinated polyolefin
Using 65 parts of styrene, 20 parts of 2-ethylhexyl acrylate, 5 parts of hydroxyl ethyl acrylate, 4 parts of ethyl acrylate, and 1 part of acrylic acid in the presence of 5 parts of styrene (dissolved in toluene, solid content 20%). Polymerization was carried out in the same manner as in the preparation of alkenylbenzene polymer (A-1) to obtain an aqueous resin composition by emulsion polymerization with a nonvolatile content of 40%.

Evaluation method> The aqueous resin composition prepared above was
(polypropylene manufactured by Japan Petrochemical Co., Ltd.) and Noblen 440GFJ (polypropylene manufactured by Mitsubishi Yuka Co., Ltd.) panel samples with a thickness of 200 μm were coated, dried at 80°C x 30 ml in a ventilation dryer, and cooled to room temperature for 3 hours. After curing, cellophane tape was peeled off using goban eyes.

<Evaluation Results> The evaluation results of the compositions in Examples 1 to 15 are shown in Table 2.

Table 2 Comparative Examples 1 to 6 Comparative Example 1
-6 aqueous resin compositions were obtained.

<Evaluation Results> Evaluation was performed in the same manner as in the examples. The results are shown in Table 4.

Table 4 (Consideration) Referring to Table 2 and Table 4, Examples 1 to 1 of the present invention
In contrast to No. 15, no peeling of the goban eyes was observed due to cellophane peeling due to the goban eyes.

Comparative Examples 1 to 6 using an alkenylbenzene-based polymer (A-3) containing only 50% or less of styrene and other resins containing no alkylbenzene (A-4) are as shown in Table 4. Significant peeling of the eyes.

(c) Effects of the Invention As detailed above, the aqueous resin composition of the present invention exhibits strong adhesion to polyolefin base materials without pretreatment with a primer or the like. It can greatly contribute to workability including process improvement, cost reduction, etc., and is excellent as a coating agent, adhesive, etc.

Claims (1)

[Claims] 1 to 100 parts by weight of a chlorinated polyolefin having a degree of chlorination of 20 to 45% by weight per 100 parts by weight of an alkenylbenzene polymer in which 50% by weight or more of the monomers constituting the polymer are alkenylbenzene. An aqueous resin composition characterized by containing