JPS5845247A - Primer composition for polyolefin material - Google Patents

Abstract

PURPOSE:The titled composition having improved state of a film and adhesiveness, obtained by blending chlorinated polypropylene with a polyacrylamine, a phenolic resin and an epoxy resin in a liquid state. CONSTITUTION:10-70pts.wt. chlorinated polypropylene (having a molecular weight of preferably 20,000-100,000) having a chlorination ratio of 20-40wt% is blended with 20-85pts.wt. polyacrylamine (preferably having a molecular weight of 10,000-50,000 and an amine equivalent of 15-30), 5-40pts.wt. phenolic resin, and an epoxy compound (an epoxy equivalent of 100-300) containing at least two epoxy groups in the molecule in an amount to give a ratio of the amine equivalent of the polyacrylamine to the epoxy equivalent of the compound (amine equivalent/epoxy equivalent) of 2.0-0.5, to give a liquid dispersed mixture. The composition is properly dissolved in an organic solvent and coating is carried out. When it is stored after its preparation, a two-pack stype composition wherein the epoxy compound is preserved separately and added to it just before coating is better.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a primer composition K with excellent coating film condition and adhesion when applied to BoIJ olefin materials. Examples of polyolefin materials include polyethylene, polypropylene, ethylene-propylene copolymer and There are modified products obtained by copolymerizing or adding other copolymerizable heptamers to these. These materials have good chemical resistance, are lightweight,
Although it has characteristics such as low cost, it is originally crystalline poly! - Since it has a low surface energy, the adhesion of paints containing organic resin as a film-forming element is generally extremely poor.

In order to improve such poor adhesion, conventional treatments such as chemical treatment, flame treatment, and electric discharge treatment have been attempted on the surface of polyolefin materials, but each method has advantages and disadvantages and has not yet reached a satisfactory stage.

On the other hand, many of the primer paints already in practical use #i contain modified polyolefins as the adhesion-imparting component;

&) Chlorinated polypropylene b) Chlorinated polyethylene a) Ethylene/vinyl acetate copolymer 11) II
I-added ethylene/propylene copolymers and the like are known. The composition of the primer paint is as follows.
, C) straddle d) and normal II! By mixing resins for one component (for example, acrylic resins and polyester resins), it provides functions that satisfy the paint properties and film performance, and
- Provides suitability for painting.

However, such primer paints generally belong to the volatile drying lacquer type paints, so they have low AM strength and poor anti-corrosion resistance.
It has the disadvantage of poor machinability and chemical resistance. In order to improve this, we introduced amino groups into acrylic polymers,
A method has been proposed in which a crosslinking agent (curing agent) such as an epoxy compound is added to form a crosslinked portion to improve the strength of the coating film.

However, the functional acrylic polymer and crosslinking agent described above each have polar groups in their molecules, resulting in decreased solubility, and simply mixing these components will result in poor storage stability and 1.
! This will cause significant defects in the properties of the paint/m film, such as the smoothness and transparency of the i-film (the degree of opacity), and the adhesion to polyolefin materials will also deteriorate, making it impossible to use. The present inventors have conducted extensive research to improve the defects in paint/m film properties caused by poor compatibility as described above, and have obtained positive results using polyoletwin, polyacrylamine, and an epoxy compound as a crosslinking agent. By blending phenolic resin in addition to the other components, we succeeded in significantly improving the compatibility between the components, resulting in good paint properties after coating, forming a uniform and smooth coating film, and polyolefin-based The present invention provides a primer composition that has excellent adhesion to materials.

N)jJ [10 to 70 parts (parts by weight,
same as below).

←) Bo IJ Acrylic 2nd 20-85 copies.

(c) 5 to 40 parts of phenolic resin, and (b) the BoI
+ 7 amine equivalent of kryluane and epoxy m of an epoxy compound containing at least two epoxy groups in the molecule
The ratio of f (Amount/Epoxy amount) is 2.0 to 0.5
This invention relates to a primer composition for olefin-based materials comprising a portion of the epoxy filler in a proportion of .

In the present invention, the II olefin material refers to a polymer of ethylene, propylene, pudene, etc. or a copolymer thereof, or a part of the molecular skeleton of a polymer or copolymer thereof having a polar group ( For example, it refers to a flammable material into which a carboxyl group has been introduced, or a modified polymer containing a copolymer component of another copolymerizable heptamer in these polymers. Such polyolefin materials are subjected to conventional degreasing and cleaning treatment as a step before coating with the primer composition of the present invention.

The chlorinated polypropylene used in the present invention is:

It is a polymer of propylene with a chlorine strength of 20 to 40, preferably 25 to 50, and its molecular structure is
It may be attic, atactic, syndiotactic, or syndiotactic, and those with a number average molecular weight of 20,000 to inn, oon are preferably used. Specifically, products manufactured by Toyo Kasei Kogyo Co., Ltd. under the trade name Heart°ren 15LLB (60% chlorine work), 14LLB (27% chlorine) and 3LLB (
Section 26), manufactured by Yamaba Kokusaku Pulp Company, product name Super Chron 8n3M (chlorite ratio 3nl), same 8
There are r13L (264) and others. The amount of the chlorinated polypropylene in the primer composition ranges from 10 to 70 parts, preferably from 15 to 55 parts. In addition, when blending, polyacrylamine, which is one of the components of the composition of the present invention, is used after being dissolved in an aromatic hydrocarbon solvent (for example, toluene). A copolymer of (meme)acrylic acid ester containing a class aquine group,
Number average molecular weight 10. OOO to 5n, nnO, aquinone with a specific weight of 15 to 50 are preferably used.The glass transition temperature is in the range of -50 to 90℃, and aromatic solvents (ja It is used in the form of a solution dissolved in aliphatic alcohol). Specifically, Kotax LK-720 (Amine Company 18.5), Kotax LK-724 (7 Min Nao fF1) made by Toshi Company, etc.
18.5), LK-74 [1 (7min #18.5)
) There are also two. Then, as the formulation I in the primer composition of the above polyacrylamine, the resin solid content is 20 to 20.
It is used in an amount of 85 parts, preferably in a range of 40 to 80 parts.

As an epoxy compound that functions as a crosslinking agent for poly(7-di-I)+luamine, 1=1. Epoxy having two or more epoxy groups in the molecule preferably f100 to 300% 140
~250 is preferably used.

For example, sorbitolbo 11g 11sigil edel can be mentioned. Specifically, for example, the product name Bunacol EX-611 (a tetrafunctional poxy compound, supplied by Nagashio Sangyo Co., Ltd.)
It has an epoxy equivalent weight of 170).

The ratio of amine equivalent/epoxy equivalent when adding polyacrylic 7-layer to the above-mentioned epoxy compound may be selected in theory so that 1.0 or a slight excess of epoxy groups exists; Curability of the Kl Goblimer composition,
2.0 to 0.5 from the perspective of usage time limit (pot life), etc.
, U is preferably in the range of 1.5 to 1.0, and the amount of the epoxy compound is set so that the proportion falls within this range.

Next, let's talk about phenolic resin, which is an important component of the present invention! Shine brightly. The phenolic resin in the present invention and the
It is a polymeric compound with a basic skeleton formed by addition and condensation of phenol or its derivatives and formaldehyde, and can be classified into novolac type and resol type depending on the form of the condensation reaction. There are also products modified by reacting rosin or ester gum with hydroxyl groups in resin molecules. Phenol derivatives and 1, Teke, those with substituents introduced at the ortho or para positions 73! There are %flIt substituents such as alkyl groups.

There are phenyl bases. As a furkyl group, a methyl group,
Ethyl group, n-butyl group, t-butyl group.

In the present invention, any novolak type or resol type phenolic resin having a car-dimensional or two-dimensional structure that is soluble in organic solvents can be suitably used, and there is no restriction on one type.
No K. Specific examples of such phenol IIM resins include nine-to-ege novolac type p-n-7' tilphenol resin, novolac type p-phenylphenol resin, and rosin-modified phenol resin.

There are resol type phenolic resins. In addition, use [A71] is blended in the form of a solution such as an organic solvent.

The blending amount of the phenol resin used in the primer composition of the present invention is in the range of 5 to 40 parts, preferably Fil.
It is o-35 parts. When the amount of the phenol resin blended is less than 5 parts, the effect of improving the compatibility between the chlorinated polypropylene, polyacryl 7one, and the epoxy compound, and the effect of adhesion with the polyolein-based material -F are reduced. tta4
If the amount is more than 0 parts, defects such as poor adhesion with the Bo11 olefin material and deterioration of tM properties may occur.

In the present invention, the composition of each of the above-mentioned components is finally prepared in the form of a liquid vehicle using an organic solvent. , usage time Vi2 [1] without diluting the coating viscosity
℃ for about 24 hours. In addition to the components of January 1, l! Pigments, dispersants, and coating surface conditioners to provide the properties and performance normally required for F-slant.

Known auxiliary agents or additives such as curing accelerators can be optionally blended.

The primer composition of the present invention can be easily produced by blending the components listed in -F to form a liquid mixture and dispersing this by a known dispersion method. If the product is to be stored after production, it is advisable to separate the epoxy compound in advance so that it can be mixed into the coating equipment (using a two-component type). For painting, the primer composition is mixed with an organic solvent (for example, toluene/ethyl acetate/methyl ethyl+). l/
After diluting to a viscosity suitable for 4 coats (2° if ratio), it can be applied without any problems by applying air spray, airless spray, electrostatic spray, or roll coating.

Although the primer composition of the present invention dries and hardens at room temperature,
It can also be dried by heating if desired.

In the case of heating drying, heating conditions for 10 to 45 minutes at temperatures below the heat deformation temperature of the polyolefin material, for example 60 to 80° C., are preferably employed.

In order to more specifically observe the content of the present invention, test examples, production examples, examples, and comparative examples are shown below.

1. Compatibility and adhesion test examples for resin vehicles Table 1 shows various #1-coated BoQ propylene/Boll II Ac 1
1 shows the results of two compatibility tests of the luain/phenol resin/epoxy compound system and an adhesion test of the coating with the polypropylene material.

Note that the chlorinated polypropylene was dissolved in toluente so as to have a predetermined solid content (4).

The blending value of each component is the solid content (parts) of each component.

■Phenol resin PP-3120: Novolamized butyl phenol resin (
*9 manufactured by Sakae Kagaku Kogyo Co., Ltd., molecular weight approximately 760) Talanol 145: Novolac type rosin-modified phenol resin (manufactured by Arayo Kagaku Koshu Co., Ltd.) OHM-n9n9: Novolac type nonylphenol resin (manufactured by Showa Union Company) Hitanol 2501 Niresol type phenol resin 81 (
(manufactured by Hitachi Chemical Co., Ltd.) MP 120: / Bojyri [: Phenol resin (manufactured by Gunei Chemical Co., Ltd.) ■Denacol EX-611: Tetrafunctional epoxy compound (supplied by Nagashio Sangyo Co., Ltd.)

Epoxy quantity 170) ■In the compatibility test, the sample was spread on a glass plate, and after drying, the coating state and IIWIi state were examined. , cross-cut (100 pieces), and the number of remaining coating film stitches (for example, when 95 pieces is 95/100) at the cut-out area after peeling off the cellophane adhesive tape.

2. Production Example of Primer Composition Production Example 1 Kill Base A Part Kotax I, Ni-720 (Solid Content 31) 100 Rutile Titanium White 50 Carbon Black rL5 Toluene
5 methyl ethyl ketone
5 Total 160.5 The composition of the above formulation was dispersed for 24 hours in a normal ball oil to obtain a rubaseme.

Milbasem 16n, 5 parts of the following formulation Coater, Tas LK-720 (solid content 61g) 95 parts 50114 bar)'lz'nl 5LLE liquid 117 parts Polyflow (
Paint surface conditioner) o, n s part Denacol W
A total of 215.05 parts of X-611518 was mixed to obtain Primer Paint 1 having the same resin composition as Sample 1 in the Compatibility Test Examples in Table 1.

Production Example 2 1 part of phenolic resin varnish PP-31202 with a solid content of 50q6 was added to primer paint 1 while stirring to obtain primer paint 2 having the same resin composition as sample 2 in the compatibility test example in Table 1. Ta.

Production Examples 3 to 10 Following the method of Production Example 1, primer paints 3. and 3.3 with the same resin composition as Samples 3.5.7 and 9 in the compatibility test examples in Table 1 were prepared.
5.7 and 9 were obtained.

Further, according to the method of Production Example 2, primer paints 4.6.8 and 10 having the same resin composition as Samples 4.6.8 and 10 in the compatibility test examples shown in Table 1 were obtained.

6. Examples 1 to 5 and Comparative Examples 1 to 5 Each of the above primer paints 1 to 10 was diluted with a thinner having a composition of toluene/ethylene glycol monoethyl ether acetate/methyl ethyl ketone (515/2C weight ratio), and the viscosity was Cup φ4.14 at 20℃
Adjusted to be ±1 second.

Each of these diluted paints was applied to a Bogoto 1 propylene molded plate (supplied by Nippon Test Panel Company) degreased with trichlene using the air spray method to a dry film thickness of approximately 15 to 20# and heated at %80°C for 30 minutes. It was heated and dried.

Next, a polyester resin-based top coat for soft materials (manufactured by Kansai Paint Co., Ltd., trade name, paint for soft materials PG-60 white) was applied to each of these coatings so that the dry film thickness was approximately 65 to 69 degrees. It was layered and dried by heating at 80° C. for 30 minutes to obtain a test piece.

The properties of each primer paint and the performance of each sample were as shown in Table-2.

■Condition after storing diluted paint at 30°C for 5 days.

■ Gopan eye test (same method as in Table 1). Sample type 11
vkTest within 24 hours.

■After being exposed to KIO chamber at 9996RH and 50°C for 1 day, gopan eye test (method is the same as ■).

■Condition after being immersed in automobile gasoline at 20℃ for 1 hour: O ○ Normal (Excellent 2), ■ There is slight lifting of the paint film, but it recovers when left unused (Good), ΔKana C/'I cracking (Slightly poor) , × means 1 piece (defective)

Claims (1)

[Scope of Claims] B) [10 to 70 parts by weight of chlorinated polypropylene with a conversion ratio of 20 to 40% by weight, ←) Polyacrylaquine 20 to as4ts. (c) Add 5 to 40 parts by weight of phenol to the resin; Epoxy amount/Epoxy amount) is 2.0 to 0.5
A primer composition for polyolefin materials comprising parts by weight of the epoxy compound in a proportion of .