JPH0940782A - Organopolysiloxane-grafted vinyl polymer and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel organopolysiloxane-grafted vinyl polymer which has excellent stretchability, gives filmy or other moldings excellent in chemical and water resistances, is improved in surface slip properties, releasability, and antiblocking properties during molding, and is soluble even in a highly safe solvent. SOLUTION: The polymer is represented by the formula (all the groups R are at least one member selected from among 1-12C alkyls, alkenyls, aralkyls, aryls, and haloalkyls, provided that at least 50mol% of the groups R are methyl; R1 is hydrogen or acetyl; x, y, and z are positive numbers satisfying 0<x<100, 0<y<100, 0<=z<100, and (x+y+z)=100, and n is an integer of 1 to 200).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silicone graft vinyl polymer, and more particularly to a novel organopolysiloxane graft vinyl polymer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVOH) has a high gas barrier property and a high transparency, and is excellent in oil resistance and aroma retention and excellent in film, sheet, container and the like. Not only widely used as a raw material for molecular materials, it is also used to improve the oil resistance and gas barrier properties of films etc. by being covered with films and sheets, especially in this case the production of films by the casting method. It is preferred to use an EVOH solution for.

However, a film or the like produced or coated with EVOH has poor chemical resistance to pesticides and some chemicals, and may be cracked by pesticides and has sufficient resistance to moisture. Not so
There is a drawback that the gas barrier property under high humidity is reduced. Further, when a film is produced by a uniaxial stretching method using EVOH, there is a drawback that the stretch moldability is poor.

Therefore, in order to improve these drawbacks,
Method of treating EVOH with a boron compound (Japanese Patent Publication No.
20615), and a method of crosslinking with an organosilicon compound (JP-A-51-20946 and 51-5354).
No. 1 and No. 54-20058), a method of partially crosslinking EVOH has been proposed. However,
In each of these methods, the amount of cross-linking agent is small,
Since the reaction is carried out by a mixer, a roll, an extruder, etc., EVOH cannot be reformed uniformly, and there is a drawback in that sufficient properties cannot be obtained.

Therefore, as a solution to the above-mentioned drawbacks, EVOH has been proposed in which an olefinically unsaturated monomer containing an alkoxy group is copolymerized with vinyl acetate and ethylene, and then saponified to crosslink siloxane (special feature: Japanese Patent Publication No. 5-53838). However, although the siloxane-crosslinked EVOH has improved the above-mentioned drawbacks, it has been desired to improve the moldability and blocking resistance because it has poor surface slipperiness and releasability when used as a molded product. .

EVOH can be dissolved only in a highly polar solvent such as methyl ethyl ketone, N, N-dimethylformamide, etc., which is generally inferior in safety. Therefore, in the field of coating agents, EVOH is a highly safe solvent. It was required to modify so that it could be dissolved. Therefore, as a result of intensive studies on the silicone-grafted vinyl-based polymer, the present inventors have found a novel organopolysiloxane-grafted vinyl polymer and arrived at the present invention.

[0007]

Accordingly, the first aspect of the present invention is as follows.
It is an object of the present invention to provide a novel organopolysiloxane-grafted vinyl polymer having excellent stretch moldability and chemical resistance and water resistance when formed into a molded article such as a film. A second object of the present invention is that the surface slipperiness during molding, releasability and blocking resistance are good, and
It is intended to provide a novel organopolysiloxane-grafted vinyl polymer which can be dissolved in a highly safe solvent. A third object of the present invention is to provide a method for producing a novel organopolysiloxane-grafted vinyl polymer having the above characteristics.

[0008]

The above objects of the present invention have been achieved by an organopolysiloxane-grafted vinyl polymer represented by the following chemical formula 6 and a method for producing the same.

[Chemical 6] All R's in the above Chemical Formula 6 are at least one selected from an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aralkyl group, an aryl group and a halogenated alkyl group, and among all R's, 50% by mole or more is a methyl group.

Specific examples of R include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group, alkenyl groups such as vinyl group and allyl group, benzyl group, phenethyl group and 2-methyl group. Aralkyl group such as 2-phenylethyl group, aryl group such as phenyl group and tolyl group, chloromethyl group, 3-chloropropyl group,
Examples thereof include halogenated alkyl groups such as 3,3,3-trifluoropropyl group.

When the methyl group in all R's in the above Chemical Formula 6 is less than 50 mol%, the mold releasability, water repellency or blocking property (these characteristics are referred to as molding characteristics) when a molded product is obtained. descend. R'in the above Chemical Formula 6 is a hydrogen atom or an acetyl group, x, y and z are 0 <x <100,
0 <y <100, 0 ≦ z <100, and x + y + z
= 100 is a positive number. That is, x, y and z are
It represents the mol% of each component. From the viewpoint of improving the molding characteristics, x is 30 to 50 and y is 0.1 to 3 in particular.
0 and z are preferably 0 to 70. N in Chemical formula 6 is an integer satisfying 1 ≦ n ≦ 200. When it is less than 1, the molding characteristics are not sufficient, and when it exceeds 200, the polymer is not suitable for production.

The organopolysiloxane graft vinyl polymer of the present invention comprises a compound represented by the following chemical formula 7 and the following chemical formula 8
It is preferably produced by reacting with a compound represented by

[Chemical 7]

Embedded image R, R ′, x, y, z and n in the above Chemical Formulas 7 and 8 are the same as those in the above Chemical Formula 6.

The compound represented by the above chemical formula 7, which is a raw material for the organopolysiloxane-grafted vinyl polymer of the present invention, is an ethylene-vinyl acetate copolymer obtained by saponifying an ethylene-vinyl acetate copolymer by a known means. It is a polymer saponification product (EVOH), which may be a partial saponification product. The molecular weight and ethylene content of EVOH are not particularly limited, but the ethylene content is 30% or less.
It is preferable to use the one of about 50% by weight. If it is less than 30% by weight, the tackiness is so strong that it is not suitable for production.
If it exceeds 50% by weight, the resulting polymer becomes hard and brittle.

Preferred examples of such EVOH are, for example, EP-F101, EP-H101 and EP.
-E105, EP-G110 (all are trade names manufactured by Kuraray Co., Ltd.), Soarnol A, Soarlite (all are trade names manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

The compound represented by the chemical formula 8 is a one-terminal isocyanate organopolysiloxane for grafting an organopolysiloxane onto EVOH, which is appropriately selected from known one-terminal isocyanate organopolysiloxanes for use. can do. Examples of such one-terminal isocyanate organopolysiloxanes include compounds represented by the following chemical formulas 9 to 14. In each formula, Me represents a methyl group, Ph represents a phenyl group, and n-Bu represents an n-butyl group.

[0015]

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[Chemical 12]

[0016]

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[0017]

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The reaction is carried out with the compound represented by the above chemical formula 7
It can be carried out by heating and mixing the compound represented by the formula (1) with or without a solvent. When the reaction is carried out in an organic solvent, the reaction temperature and time are usually 3
Although it is 0.5 to 20 hours at 0 to 180 ° C., in order to lower the reaction temperature to 30 to 150 ° C., a urethanization promoting catalyst such as dibutyltin acetate, dibutyltin dioctoate, dibutyltin dilaurate or the like can be used. .

The reaction temperature and time in the absence of solvent are usually 8
It is 2 to 60 minutes at 0 to 220 ° C., but if necessary,
The reaction temperature can be lowered by using a tin catalyst.
The reaction in this case is preferably carried out using a heating reaction device such as a single-screw or twin-screw extrusion kneader, a heating roll, a gate mixer, a planetary mixer, and a plastomill.

Further, the reaction has a silicone modification rate of EVO.
It is preferable that the amount of H is 2 to 60% by weight. If it is less than 2% by weight, the molding characteristics of the polymer obtained are not sufficient, and if it exceeds 60% by weight, the strength of the molded article such as a coating or film produced by the polymer obtained is insufficient.

As the organic solvent, N, N-dimethylformamide (DMF), methyl ethyl ketone (ME
K), polar solvents such as methyl isobutyl ketone, and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and the like. Among these, DMF is particularly preferably used from the viewpoint of reactivity and solubility.

When the organopolysiloxane-grafted vinyl polymer of the present invention is used as a coating agent, it is preferable to use a product obtained by reacting in an organic solvent, while when it is used for a film or the like, an organic solvent is used. It is preferable to use a polymer obtained by reacting without a solvent, rather than using a polymer obtained by distilling off the solvent.

Further, the organopolysiloxane-grafted vinyl polymer of the present invention is reacted with the compound represented by the following chemical formula 15 and the compound represented by the chemical formula 8, and then the remaining alcoholic hydroxyl group is treated with an acetylating agent. It is also a preferable method to produce by acetic acid esterification.

Embedded image X, y and z in the above Chemical formula 15 are the same as those in the above Chemical formula 6. The compound represented by the above Chemical formula 15 is also EVOH.

Examples of the acetylating agent include acetic anhydride and acetyl chloride. In the case of using acetic anhydride, the acetic acid esterification reaction is carried out without solvent or in an organic solvent at 50
It can be performed at ~ 120 ° C. On the other hand, when acetyl chloride is used, it can be carried out at 50 to 120 ° C. in an organic solvent in which a hydrochloric acid scavenger such as triethylamine or pyridine is present, but from the viewpoint of ease of reaction, acetic anhydride is used. Preference is given to using. As the above-mentioned organic solvent, the same ones as those used for reacting the compounds represented by Chemical formulas 7 and 8 can be used.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The organopolysiloxane-grafted vinyl polymer of the present invention has excellent moldability, water repellency, weather resistance, and heat resistance as materials for films, sheets, containers, and the like.
Further, since it has excellent solubility in a solvent as a protective coating material for metals, ceramics, and glass products, it is effective as a coating agent for imparting lubricity, releasability, water repellency, and the like.

The organopolysiloxane graft vinyl polymer of the present invention is a thermoplastic resin such as ABS, vinyl chloride, polystyrene, polyethylene, polypropylene, polyacetal, PET, PBT, P-MMA, or an epoxy resin, a phenol resin. , Melamine resin,
As an additive for imparting moldability, mold releasability, cold resistance, impact resistance, etc. to thermosetting resins such as unsaturated polyester resins and urethane resins, further, concrete, mortar, slate, etc. It is also useful as an internal addition type water repellent or mold release agent that imparts water repellency, weather resistance, mechanical strength, etc. to an inorganic material.

[0027]

The organopolysiloxane-grafted vinyl polymer of the present invention is a novel polymer obtained by graft-polymerizing a specific amount of organopolysiloxane on EVOH.
When used as a molded product such as a film, it has excellent chemical resistance, water resistance and stretch moldability, and has improved surface slipperiness, mold release and blocking resistance during molding, and is used as a coating agent. If you do, ethyl acetate, M
It can also be dissolved in highly safe solvents such as IBK, toluene, xylene, and MEK. Further, according to the production method of the present invention, the novel organopolysiloxane graft vinyl polymer of the present invention can be easily produced.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 In a 1-liter flask, the average composition formula is (CH ₂ —CH ₂ ) ₄₄ (CH ₂ —CH (O
H)) Eval resin represented by ₅₆ (Soarnol A-44
12: trade name of Nippon Synthetic Chemical Industry Co., Ltd.) 14 g, N,
40 g of N-dimethylformamide and 6 g of an isocyanate silicone having one terminal represented by the above chemical formula 10 were charged and reacted at 90 ° C. for 6 hours to obtain a slightly yellow and uniform reaction solution. 20 g of DMF in the obtained reaction solution
And 20 g of MEK were added to obtain a cloudy dispersion.

The obtained dispersion was applied to a mild steel plate having a thickness of 0.3 mm by using a bar coater No36 and dried at 105 ° C for 30 minutes to form a coating film. The result of measuring the infrared absorption spectrum of the obtained coating is as shown in FIG. From the results of this spectrum, it was confirmed that the obtained substance was the polymer of the present invention represented by the following chemical formula 16.

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Next, the following physical properties of the coating were measured and evaluated. The results are shown in Table 1. The appearance of the coating was visually evaluated. Pencil hardness It was performed in accordance with JIS K-5400 (1990 version), item 8-4. Water contact angle meter
(Trade name of Kyowa Interface Science Co., Ltd.) was used. Dynamic friction coefficient Using a dynamic friction coefficient measuring device (trade name of Kyowa Interface Science Co., Ltd.), a SUS ball with a load of 50 g and a speed of 10 c
It was measured under the condition of m / sec. Conforming flexibility JIS K-5400 (the 1990 edition) 8-1 Section was measured using a mandrel bending resistance tester (2 mm). Impact resistance The impact resistance was measured using a DuPont type impact resistance tester (measurement conditions: ½ inch ball 500 g, height 50 cm) in accordance with JIS K-5400 (1990 version) item 8-3.

[0032]

[Table 1]

Example 2 To a 1-liter flask, 30 g of the reaction solution obtained in Example 1 and 3 g of acetic anhydride were added, and the mixture was heated at 80 ° C. for 4 hours to obtain a reaction solution. The solvent of the obtained reaction solution and unreacted acetic anhydride were distilled off under reduced pressure to isolate a rubber-like elastic material. The obtained elastic substance was easily dissolved in MEK and almost dissolved in toluene, although it was slightly turbid. The raw material Soarnol is ME
It was insoluble in both K and toluene.

The obtained solution was used to form a film in the same manner as in Example 1 and the infrared absorption spectrum was measured. The results are shown in FIG. From the results of this spectrum, it was confirmed that the obtained substance was a polymer represented by the following chemical formula 17.

Embedded image Further, in the same manner as in Example 1, the physical properties of the film were measured and evaluated, and the evaluation results are as shown in Table 1.

Example 3. Labo Plastmill (trade name of Toyo Seiki Seisakusho Co., Ltd.) and EVAL resin (EP-E1
05: Trade name of Kuraray Co., Ltd .: (Ethylene / PV
A) has a molar ratio of 44/56 and a softening point of 165 ° C) 60 g
And 3 g of one-sided isocyanate silicone represented by the above Chemical Formula 12, kneading at 170 to 180 ° C. under a nitrogen gas atmosphere, and reacting for 10 minutes to give N350 of 2350 ⁻¹ cm.
After confirming that the absorption wavelength of CO has disappeared,
A polymer represented by 8 was obtained.

Embedded image DM was added to the obtained polymer so that the active ingredient was 20%.
It was dissolved in a mixed solution of F and MEK (DMF / MEK = 50/50 weight ratio), a coating was provided in the same manner as in Example 1, and physical properties of the coating were measured in the same manner as in Example 1. The evaluation results are as shown in Table 1.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the polymer of the present invention obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the polymer of the present invention obtained in Example 2.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akira Yamamoto 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronic Materials Technology Laboratory, Shin-Etsu Chemical Co., Ltd.

Claims (3)

[Claims] 1. An organopolysiloxane-grafted vinyl polymer represented by the following chemical formula 1; However, all R's in Chemical Formula 1 are at least one selected from an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aralkyl group, an aryl group, and a halogenated alkyl group, and 50 mol% or more is a methyl group, R'is a hydrogen atom or an acetyl group, and x, y and z are
0 <x <100, 0 <y <100, 0 ≦ z <100, respectively
And a positive number satisfying x + y + z = 100, and n is 1 ≦
It is an integer that satisfies n ≦ 200. 2. A method for producing an organopolysiloxane-grafted vinyl polymer, which comprises reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3; Embedded image However, R'in Chemical formula 2 is a hydrogen atom or an acetyl group, x, y
And z are 0 <x <100, 0 <y <100, 0 ≦, respectively.
z <100 and a positive number satisfying x + y + z = 100, and all Rs in Chemical formula 3 are from an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aralkyl group, an aryl group and a halogenated alkyl group. It is at least one kind selected, and 50 mol% or more of all R are methyl groups, and n is an integer satisfying 1 ≦ n ≦ 200. 3. An organopolyamide characterized by reacting a compound represented by the following chemical formula 4 with a compound represented by the following chemical formula 5, and then acetic acid esterifying the remaining alcoholic hydroxyl group with an acetylating agent. Method for producing siloxane-grafted vinyl polymer; Embedded image However, x, y and z in Chemical formula 4 are 0 <x <100,
0 <y <100, 0 ≦ z <100, and x + y + z
= 100, and all Rs in Chemical formula 5 are at least one selected from alkyl groups having 1 to 12 carbon atoms, alkenyl groups, aralkyl groups, aryl groups, and halogenated alkyl groups. In addition, 50 mol% or more of all R are methyl groups, and n is an integer satisfying 1 ≦ n ≦ 200.