JPH01319518A - Silicone/acrylic copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, having film-forming properties and providing the formed films excellent in surface characteristics by polymerizing a compound expressed by a specific formula with (meth)acrylic acid ester and carboxyl group-containing monoethylenically unsaturated monomer in respective prescribed proportions. CONSTITUTION:The objective composition obtained by polymerizing 10-60wt.% compound expressed by formula I [X is radically polymerizable group (optimally methacryloxy group); R<1> is 1-20C monofunctional hydrocarbon (optimally CH3), 1-20C monofunctional halogenated hydrocarbon or formula II (R<2> is 1-20C monofunctional hydrocarbon or monofunctional halogenated hydrocarbon; p is 5-100), provided that the number of a group expressed by formula III in R<1> is 0, 1 or 2; m is 1-10; n is 5-100] with (B) 25-75wt.% (meth)acrylic acid ester and (C) 5-20wt.% carboxyl group-containing monoethylenically unsaturated monomer [provided that the total amount of the component (A), (B) and (C) is 100wt.%] in the presence of a radical polymerization initiator and consisting essentially of a silicon/acrylic copolymer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silicone/acrylic copolymer composition, specifically a non-crosslinkable one that dissolves in general-purpose solvents such as alcohol and swells in weak alkalis. Silicone/acrylic copolymers, which are useful for film formation, are mainly used because they have good compatibility with other resins, have practical film-forming properties, and the films formed show excellent surface properties. It relates to a composition containing it as an ingredient.

(Conventional technology) As a general-purpose silicone oil, dimethylpolysiloxane has properties such as heat resistance, light resistance, water resistance, chemical resistance, lubricity, water repellency,
It is non-adhesive, anti-foaming, and physiologically inert, and is widely used in industrial, household products, medicine, cosmetics, etc., and because it is liquid, it cannot form a film on its own. Insoluble in hydrophilic solvents such as lower alcohols and glycols,
It is insoluble in water at any pH and cannot be emulsified by itself.

Because it has extremely poor compatibility with other substances, it is difficult to mix uniformly, and it separates and bleeds from the blended composition, causing not only its performance to change over time, but also to migrate to solid surfaces that come into contact with it. If the surface that has been in contact with the coating does not like the characteristics of silicone oil (slimy feel, slipperiness, non-adhesion, water repellency, non-reapplicability, etc.), this is so-called silicone contamination. In particular, for products that are made into rolls (wallpaper, adhesive tapes, packaging materials, etc.), the back side is dyed with 45 dyes using silicone oil in the surface treatment layer or rolled to give the back side the necessary performance (adhesiveness).

printability, etc.). It is extremely difficult to completely remove silicone oil from surfaces once it has adhered, and requires the use of strong solvents, so it cannot be removed from plastic substrates that cannot withstand strong solvents, and water or alcohol cannot be used. This is extremely inconvenient at home. Surfaces coated with silicone oil tend to attract dust, and attached dust is difficult to remove.

On the other hand, silicone polymers with film-forming properties include
Polymers made by copolymerizing silicone macromers and methacrylic acid esters as shown in graph 1 have been known for some time, and these can make paints etc. highly weather resistant or improve the l1lii type properties of adhesive tapes etc. It was aimed at such things.

Many commercially available polymers of this type utilize the terminal groups of acrylic/silicone copolymers to crosslink, and the crosslinked polymers do not dissolve in alcohols.

In addition, polymers with a high silicone content do not form a film and become oily, resulting in poor adhesion to the substrate, being susceptible to static electricity, and easily attracting dirt, which is difficult to remove.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks and improves the surface properties of silicone oil (lubricity, water repellency, non-adhesiveness).

It takes full advantage of the properties (non-reapplicability, stability, etc.) and can form a film by itself. It has moderate adhesive strength to other substrates. It is soluble in lower alcohols, making it practical and easy to use, and it is easy to remove from the substrate surface. Compatible with other substances, general polymer substances, and dimethylpolysiloxane oil.

Avoid contact with other substances (contamination). Easily swells with weak alkalis such as amines and aqueous ammonia, and can be removed from the substrate. Dust is less likely to adhere to surfaces than silicone oil coated surfaces. It can be used as an auxiliary agent to stably disperse dimethylpolysiloxane, which is insoluble and non-dispersible in lower alcohols, in lower alcohols.

This was done in order to provide a composition whose main component is a silicone/acrylic copolymer that has the following characteristics.

(Structure of the Invention) As a result of extensive research by the present inventors to achieve the above object, it has been discovered that the silicone/acrylic copolymer synthesized by the present inventors may be suitable for this purpose. Based on this knowledge, they conducted further studies and arrived at the present invention.

The composition of the present invention achieves the above object, and is characterized by (A)-forming [where X is a radically polymerizable group and R1 has 1 to 20 carbon atoms]
monovalent hydrocarbon group, monovalent halogenated hydrocarbon ~ 1 of 20
One or more groups selected from the following groups (where p is an integer of 5 to 100), a valent hydrocarbon group or a monovalent halogenated hydrocarbon group; 10 to 60% by weight (B
) Acrylic acid ester or methacrylic acid ester 25 to 75% by weight and (C) carboxyl group-containing monoethylenically unsaturated monomer 5 to 20% by weight (Tap, (A) + (B) + (C) - The main component is a silicone/acrylic copolymer obtained by polymerizing 100% by weight) in the presence of a radical polymerization initiator.

Among the monomer components constituting the silicone/acrylic copolymer that is the main component of the composition of the present invention, component (A) has the general formula % as described above. Particularly preferred are methacryloxy and acryloxy groups. If m is too large, the effect of the silicone (organopolysiloxane) will be hindered, so m is an integer from 1 to 10, but 3 is typical. When R1 does not contain silicon, R1 is a methyl group, an ethyl group,
Examples include a phenyl group, a trifluoropropyl group, and a methyl group is preferred. Examples of R2 include the same groups as R1 when it does not contain silicon. If the R1 formula orcap polysiloxane is too small, the characteristics of organopolysiloxane such as lubricity, water repellency, and non-adhesion will not be exhibited, and if it is too large, the performance will deteriorate in terms of alcohol solubility, film forming properties, etc. Therefore, n and p are each in the range of 5 to 100. And (A
) The following are exemplified as monomers of the component.

II jl 0 11Jb CH3 E+t+ 3C) 13 cl2-cl OCCH25l--koO5t〒cH3
(n-20)0 C83CI+3 al13CI+3 CH2-CH-C117Si←05ih "Cll3
(n-25) CH3CH3 Component (A) gives the copolymer the advantages that polysiloxane has, but if it is too small, these advantages will be insufficient, and if it is too large, it will improve film-forming properties, compatibility with other substances, etc. Since the adhesion of components (A) to (C) is lost, it is necessary to set the amount to 10 to 60% by weight of the total amount of components (A) to (C).

Component (B) is an acrylic ester or methacrylic ester, or its alcohol component has 1 to 1 carbon atoms.
18 alkyl groups or alkoxy-substituted alkyl groups are used, specifically, acrylic acid or methacrylic acid with methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, methoxyethyl, and methoxybutyl alcohols. Examples include esters.

Component (B) has solvent solubility, film-forming properties, compatibility with the copolymer,
It provides adhesion to other materials and allows the flexibility of the coating to be adjusted over a wide range. The (meth)acrylic acid ester of component (B) does not impair the excellent heat resistance and light resistance of the organopolysiloxane. In order to take advantage of the properties of this component (B) and not impair other useful properties, the amount of component (B) must be 25 to 75% of the total amount of components (8) to (C). or is necessary.

Component (C) is a carboxyl group-containing monoethylenically unsaturated monomer, including acrylic acid, methacrylic acid,
Examples include chronic acid, itaconic acid, maleic acid, fumaric acid, maleic acid half ester, and fumaric acid half ester.

In addition to having the same functions as component (B), component (C) further increases adhesive strength to the base material, lowers charging properties, and provides swelling or dispersibility in weak alkalis such as amines and aqueous ammonia. , which further facilitates the removability of the copolymer. Too much water repellency.

The amount of component (C) needs to be 5 to 20% by weight of the total amount of components (A) to (C), since it reduces water resistance and makes the film hard.

The silicone/acrylic copolymer used in the present invention can also be copolymerized with monomers other than the above-mentioned components (A) to (C). namely, vinyl chloride, styrene, acrylonitrile, vinylidene chloride, vinyl acetate, and 2-hydroxyethyl methacrylate.

N-methylol acrylamide, acrylamide]・.

Of course, it is also possible to further copolymerize vinyl monomers such as glycidyl methacrylate. However, in order not to spoil the spirit of the present invention, (A), (B), (C)
The amount is preferably 20 parts by weight or less based on 100 parts by weight of the total amount of components.

For copolymerization to synthesize the silicone/acrylic copolymer used in the present invention, a radical polymerization initiator is used, and either solution polymerization or suspension polymerization is used.

The copolymerization method itself may be a known method. Examples of the radical polymerization initiator include dihenzoyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate, and azobisisobutyronitrile. Solvents used during solution polymerization include methanol, ethanol, isopropanol, acetone, methyl edyl ketone, ethyl acetate,
In suspension polymerization, polymeric protective colloids such as polyvinyl alcohol and methylcellulose are used as suspending agents, such as Hensen, toluene, and ethylene glycol monoalkyl ether.

The compositions of the invention are conveniently used in solution form. The solution polymerization amount can be used as is or water.

The copolymer is precipitated with ethylene glycol or the like, washed, purified, dried, and then redissolved in a solvent. The suspension polymerized amount is dissolved in a solvent after washing with water and drying. [Solvents are household products] 2 For applications as solvents, ethanol and isopropanol are preferred from a sanitary standpoint. When added to the polymer solution as a modifier for other polymers, a good solvent for the polymer is used.

Furthermore, one of the major features of the silicone/acrylic copolymer used in the present invention is that the carboxyl group derived from component (C) can be neutralized with amine or ammonia depending on the use. The unneutralized amount using component (C) is, for example, plastic or film.

Next month, when coating a substrate such as metal, the coating will swell if treated with weak alkaline water such as amine or ammonia, regardless of its excellent adhesion to the substrate, water repellency, and water resistance. It can be peeled off from the base A and completely removed. Therefore, the unneutralized amount is suitable for use in preventing stains on substrates, as a protective agent, as a polishing agent, and the like.

On the other hand, films from neutralized products, especially those from solutions neutralized with high-boiling amines, swell with neutral water and are peeled off from the base material, so they cannot be easily removed from the human body in pharmaceuticals and cosmetics. The products are convenient. Neutralization or non-neutralization does not limit the present invention and is left to the selection of the groove to be used depending on the application.

Furthermore, dyes, pigments, fillers such as silica, or other additives may be added to the composition of the present invention as long as they do not impair the purpose of the present invention.

The composition of the present invention is useful in a variety of applications, and the film formed does not attract dust like silicone, for example,
It can be used to prevent stains on PVC wallpaper, to prevent stains on furniture and automobiles, and to prevent static electricity.It can be used to provide lubricity to fiber surfaces (smooth feeling), to paint lacquer, etc., and to prevent stains on furniture and automobiles.
It can be used as base materials and covering materials for cosmetics, etc.

Wallpaper made from PVC is not widely used, but because it has static electricity, dirt tends to stick to it, and various anti-static agents have been used, but none have been found to be satisfactory. Furthermore, if marker ink or the like adheres to the surface, it cannot be wiped off sufficiently. In other words, there was a desire for a wallpaper that would not only attract dirt, but even if it did get dirty, it would be easy to wipe it off. This is not limited to car wallpaper, but by coating plastic or metal products with the composition, desirable properties can be easily imparted. In other words, it is easy to remove oil and dirt from kitchen utensils (ventilation fans, refrigerators, microwave ovens, kitchen equipment such as cupboards), etc.

As a contamination protection agent for household products, it can be applied in the form of an ethanol solution, edible oil 2 oil mist, and food (gutschup).

Stain from ink (sauce, soy sauce, etc.), crayon, marker ink, etc. is difficult to adhere to or is easy to remove. After an appropriate amount of time, the paint film can be completely removed with weak alkaline water or ethanol, and unlike silicone, it does not attract dust.

Since this composition has sufficient film-forming ability,
It can also be applied to other furniture products, blinds, and plastic or glass parts of vehicle products such as automobiles to expect the effect. It is also useful for producing car wax by utilizing its compatibility with dimethylpolysiloxane.

Pharmaceutical tablets, granules, etc. have been coated with simple acrylic polymers in the past, but coating with this composition allows for a transparent and durable film coating, with only dirt attached, and has good lubricity. This has the advantage of facilitating the manufacturing and packaging process of pharmaceuticals. Even in the case of cosmetics, these properties have enabled many fields of application, as they are pleasant to the touch and can be removed with soap. In the case of pharmaceutical and cosmetic products, it has been particularly desired to form a transparent film that is soluble in ethanol or a mixed solvent of water/ethanol, and has been made possible by the present invention.

Of course, it can be easily blended with other resins, and is useful for improving performance, such as adding lubricity to paint films, by adding it to paints, especially alcohol-based varnishes and lacquers such as shellac varnish, ethyl cellulose, and hydroxypropyl cellulose. be.

Although these performances are desired in various fields, they have not been fully realized until now, or they have been made possible by the present invention.

Examples of the present invention will now be described.

Example [Synthesis of silicone/acrylic copolymer and preparation of composition] A copolymer was produced with the monomer composition shown in Table 1 by solution polymerization in isopropanol using acetyl peroxide as a catalyst.

A closed reactor equipped with a stirrer was purged with nitrogen, 150 parts by weight of isopropanol was charged, and the inside of the reactor was adjusted to 70 tons. 1.25 parts by weight of acetyl peroxy F was added, and the following monomer mixture MAst ( Structural formula is as shown in Table 1) 50 parts by weight Methyl methacrylate
20 parts by weight ethyl acrylate
20 parts by weight methacrylic acid 1
0 parts by weight were added over 4 hours. After the addition was completed, the inside of the reactor was maintained at 80°C and stirred for 5 hours to complete the reaction.

1000 parts by weight of 40°C warm water was placed in a mixer, and the reaction solution was gradually added to the mixer while stirring with shear to precipitate the polymer, which was then filtered. Re-chill warm water at 40°C in a mixer for 10 minutes.
00 parts by weight and the filtered polymer were added, stirred with shear for 10 minutes, and then filtered. This was repeated three times and then the polymer was dried. Polymer yield was 94%. This polymer was dissolved in ethanol at a concentration of 30% to obtain a slightly yellow but almost transparent solution S-1.

S-2 and S-3 were prepared in the same manner.

As a comparative example, a copolymer containing no organopolysiloxane as listed in Table 1 was synthesized in the same manner as in the example, and a 30% ethanol solution (S-ratio -1) was synthesized in the same manner as in the example.
) was prepared.

Table 1 *MASi; One-end methacryloxypropyl-modified cymedylbolysiloxane CH3CH3CI+3 1 1 I C)I2-C-C-0-]]CH2+7Si--HO5
i-7-CH3n-25Q C
H3Cl, 3 [Evaluation of composition] The following tests 1 to 7 were conducted using solution S-1.

The results are also listed.

1. Film-forming property: Using a doctor knife, the film was applied to a clean glass plate, aluminum plate, or polyethylene glycol terephthalate (abbreviated as PET) film to a solid content of 5 g/m2, and then air-dried at room temperature. Formed a transparent, non-sticky, smooth, glossy honey film.

2. Adhesion: Cellotape was pressed onto the above film and rapidly pulled off, but the film did not peel off at all.

3. Blocking resistance.

Combine the above PET film coated products together, 0.5k
After applying a load of g/cm2 and leaving it in a constant temperature chamber at 150°C and 90% humidity for 24 hours, both sides were peeled off, and there was no abnormality in the film.

4 Water repellency, JIS-L- for the above glass plate coated product
A water repellency test using 1092 was conducted and the water repellency was 90.

5. Migration to other objects: After placing another clean glass plate on the coated glass plate and leaving it under the same conditions as the anti-blocking property,
I took out the crow board. The glass surface had no scratches at all, and when water was dropped, the water thoroughly wetted the glass surface and spread out, just as before the test. From the above, it can be seen that the film of the product of the present invention does not contaminate other substances by contact.

6. Dust from the dust collection bag of a vacuum cleaner was sprinkled on the glass plate coated product. Wiping with dry gauze removed most of the dust, and wiping with wet gauze removed it completely.

7 Removability of coating film, 2
% ammonia water and ethanol were added dropwise, and the removability of the film was observed. When using ammonia water, the film peeled off (swelled) after 2 minutes and was easily and completely removed with a cloth.

It dissolved in ethanol after 2 minutes and was completely removed with a cloth.

Tests 1 to 7 above were also conducted for S-2, 5-3, and S-ratio-1, and the results shown in Table 2 were obtained.

2 Regarding Table S-1, S-2, 5-3, 5-ratio-1, the following 8~
Ten tests were conducted.

8゜ Ethanol solubilization of dimethylpolysiloxane oil, dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd. splitting product name KF96.100cs) S-1, S-2 in lOg
, S-3°S-Ratio-1, 90 g each, were mixed and observed for separation after 5 days of standing. The results are shown in Table 3.

Table 3 9 A5 Dyeing prevention property; S-1, S-2, S on white PVC wallpaper
-3゜S-ratio-1 was applied to 587m2 in terms of solid content, and 1
After drying at 05°C for 2 minutes, it was heat-treated at 220°C for 2 minutes. A lubricated surface was obtained without any sticky feeling. Add this to a water-based pen (
black).

A line was drawn with a black oil pen and a crayon (black), and the stain prevention ability was observed using the following method.

a) Immediately after drawing, wipe with dry gauze (30 times, same applies below) b) After 30 minutes of drawing, erase with an eraser.

C) Wipe with dry gauze after 30 minutes of drawing d) Drawing 3
After 0 minutes, wipe with water-soaked gauze e) After 30 minutes of drawing,
Wipe with gauze moistened with ethanol f) After 30 minutes of drawing,
Curse cloth wet with soapy water (pHIO) judgment, 00
Completely removes dirt.

0, slightly remaining ×　・Remains quite a bit XX, Obe remains The results are shown in Table 4.

Table 4 10 Water dispersibility of neutralized product; S-1,5-2□5-3. Each solution of S-ratio-1,
Neutralization was achieved by adding an amount of monoethanolamine equivalent to the bound carboxylic acid to obtain a slightly yellow, almost clear solution. This was coated on a PET film in the same manner as above, dried, and water was added dropwise. 'After several minutes, the film swelled and peeled off, and was completely removed by wiping.

Claims (1)

[Claims] 1. (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X is a radically polymerizable group, and R^1 has 1 to 2 carbon atoms.
0 monovalent hydrocarbon group, monovalent halogenated hydrocarbon group or formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms or monovalent halogen One or more types of carbonized hydrocarbon groups, p is 5 to 100
1 or 2 selected from the groups represented by
Groups of more than one species, however, among all R^1 in the general formula, groups represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are 0
, 1 or 2, m is an integer of 1 to 10, n is 5 to 100
is an integer of 10 to 60% by weight (B) 25 to 75% by weight of an acrylic ester or methacrylic ester and (C) 5 to 20% by weight of a carboxyl group-containing monoethylenically unsaturated monomer ( However, a composition whose main component is a silicone/acrylic copolymer obtained by polymerizing (A) + (B) + (C) = 100% by weight) in the presence of a radical polymerization initiator. 2. The composition according to claim 1, wherein the silicone/acrylic copolymer is dissolved in alcohol.