JPS61215629A - Surface modifying composition - Google Patents

Abstract

PURPOSE:The titled composition which can impart excellent water repellency, slip and heat resistance, comprising a polymer obtained by copolymerizing a polymerizable silane with an unsaturated organic acid and a copolymerizable monomer in the presence of a hydroxyl group-terminated polysiloxane. CONSTITUTION:0.05-10wt% polymerizable silane compound (B) (e.g., vinyltrimethoxysilane) is copolymerized with 0.5-10wt% unsaturated organic acid (C), (e.g., acrylic or maleic acids) and 60-98.45wt% other monomers (D) copolymerizable therewith (e.g., butyl acrylate or acrylonitrile), with the total of components A, B, C and D of 100wt%, in the presence of 1-20wt% hydroxyl group-terminated polysiloxane (A) of the formula (wherein R<1> and R<2> are each a hydrocarbon and n>=1). The obtained copolymer is used as an effective component to obtain the purpose surface modifying composition.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a surface comprising a polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing a terminal hydroxyl group. This relates to a modification composition, which provides a composition that can be applied to the surface of a base material such as a film, fiber, steel plate, etc. to impart surface properties such as water repellency, slipperiness, heat resistance, and migration resistance. It is.

(Prior art) In recent years, with the development of electronic equipment, the requirements for performance such as slip properties, heat resistance, and abrasion resistance of magnetic tapes, floppy disks, thermal printing materials, etc. have become increasingly sophisticated. There is a need for a composition that meets these demands. Various improvements have been made to meet the demands for slipperiness, heat resistance, abrasion resistance, etc. These methods can be broadly divided into two types: modification of the main body of the film used as a base material for magnetic tapes and thermal printing materials, and modification by applying a modification substance to the surface.

The former method uses a heat-resistant resin film such as polyimide or polysulfone as a base material (Japanese Patent Laid-Open No. 59-1
No. 52894) has been disclosed, but it is expensive and it is difficult to obtain the thin film necessary for high functionality.

In addition, for polyester film, which is most commonly used as a base material, there is a method of generating inorganic particles during polyester production (Japanese Patent Publication No. 34-5144) or a method of adding inorganic particles such as silica or calcium carbonate (Japanese Patent Publication No. 34-5144). 42-24099, Japanese Patent Publication No. 43-12013), etc., methods for obtaining films with good slip properties have been disclosed, but these methods have problems in that it is difficult to control the particle size of generated particles and that it is difficult to obtain slip properties. It is necessary to add a large amount of inorganic particles, which reduces workability during film formation and causes problems in making the film thin and transparent. Furthermore, a method of introducing a polysiloxane containing a terminal hydroxyl group into the polyester main chain (JP-A-59-168027) has also been disclosed, but since the polysiloxane is distributed throughout the base material,
A large amount is required, and it also causes problems in the adhesion of the magnetic film or ink layer.

The latter method involves coating the surface of the substrate with silicone resin, epoxy resin, melamine resin, fluororesin, etc. to modify the surface (U.S. Pat. No. 4,310,600, Japanese Patent Publication No. 5
No. 9-39308 and JP-A No. 55-7467) have been disclosed, but they have the disadvantage that the properties aimed at improving the slipperiness and heat resistance are not compatible with the adhesion of the resin film to the base material.

In addition, a method using a silicone graft copolymer using acrylic modified silicone (Japanese Patent Application Laid-Open No. 58-15476
No. 6, JP-A No. 58-164656), it is possible to achieve both slipperiness and adhesion, but the problem remains that the production of acrylic-modified silicone is complicated and expensive.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems of the prior art, maintains adhesion to a base material in a simple manner, and provides a surface with slipperiness, heat resistance, and abrasion resistance. The present invention provides compositions that provide the

(Means and effects for solving the problem) The present inventors effectively utilize polysiloxane that has excellent heat resistance, slipperiness, and migration resistance, and also exhibits good adhesion to the base material. As a result of intensive research on surface-modifying compositions, we have found that a composition comprising a polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing a terminal hydroxyl group can be used for films, fibers, The present invention was completed based on the discovery that it has good adhesion to a base material such as a steel plate, and exhibits excellent heat resistance, slipperiness, and migration resistance.

That is, in the present invention, a polymerizable silane compound (
B) 0.05-10% by weight, unsaturated organic M(C) 0.5
-10% by weight and other polymerizable monomers (D) copolymerizable with these 60-98.45% by weight (However, (A), (
The total of components B), (C) and (D) is 10'O weight%
shall be. ) is provided.The present invention provides a surface-modifying composition comprising a polymer obtained by polymerizing .).

The terminal hydroxyl group-containing polysiloxane (A) used in the present invention has the general formula (wherein R1 and R2 are each independently a hydrocarbon group that may be substituted with a monovalent halogen, and n is an integer of 1 or more. ), and various types are currently readily available and can be used depending on the purpose. The molecular weight of the polysiloxane (A) used is preferably one in which n is in the range of 10 to 2,000.

If n is less than 10, the 1q composition will not sufficiently exhibit the desired surface properties, and if n exceeds 2000, it will become highly viscous, making handling and polymerization operations difficult, which is not preferred. In addition to the polysiloxanes represented by the general formula above, polysiloxanes having partially branched side chains can also be used as the polysiloxane (A) without any problem.

The amount of the terminal hydroxyl group-containing polysiloxane (A) can be adjusted as appropriate within the range of 1 to 20% by weight, depending on the degree of surface modification.

If the amount is less than 1% by weight, the surface properties will not be sufficient, and if it exceeds 20% by weight, the adhesion to the substrate will decrease, which is not desirable.

The polymerizable silane compound (B) used in the present invention is a compound having in its molecule at least one polymerizable unsaturated group and at least one group capable of condensation reaction with the polysiloxane. Methoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane , γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyljethoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane, 2-styrylethyltrimethoxysilane , (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, etc., and one type or a mixture of two or more types selected from these groups is used. can do.

The amount of the polymerizable silane compound (8) to be used can be determined as appropriate within the range of 0.05 to 10%.

In amounts less than 0.05% by weight, polysiloxane (A
) and the polymer consisting of components (B), (C), and (b) are insufficiently bonded, so that an effective amount of graft reaction does not occur, and the composition tends to undergo layer separation.

Furthermore, if the amount exceeds 10% by weight, gelation during polymerization tends to occur, resulting in poor stability of the composition.

The unsaturated organic 112 (C) used in the present invention has the effect of inducing a bond between the polysiloxane (A) and the polymer to smoothly proceed with the grafting reaction, and also increases the adhesion of the resulting composition. Examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and unsaturated sulfonic acids such as vinylsulfonic acid, sulfoethyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid. One or a mixture of two or more of these can be used.

The amount of unsaturated sulfuric acid (C) to be used can be determined as appropriate within the range of 0.5 to 10% by weight. If the amount used is less than 0.5% by weight, it is difficult to cause an effective amount of the graft reaction, and if the amount used exceeds 10% by weight, it becomes difficult to maintain the balance between the polymerization reaction and the grafting reaction, and the resulting composition This will impair surface modification effects such as water repellency and slipperiness, as well as adhesion.

Examples of the polymerizable munitions (D) used in the present invention include acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; methacrylic esters such as methyl methacrylate and butyl methacrylate; vinyl acetate; , vinyl esters such as vinyl propionate; aromatic vinyls such as styrene and vinyltoluene; unsaturated nitrites such as acrylonitrile and methacrylate; unsaturated amides such as acrylamide and N-methylolacrylamide; ethylene, propylene, isobutylene α-olefins such as; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether; vinyl chloride, vinylidene chloride, vinyl fluoride,
Halogen-containing α, β-unsaturated monomers such as vinylidene fluoride; trifluoroethyl (meth)acrylate, 2.2.
3.3-tetrafluoropropyl acrylate, IH,
Fluorine-containing (meth)acrylic acid esters such as IH, 21(,2H-hebutadecafluorodecyl acrylate IH, 5H-octafluoropentyl acrylate); 2,3.5.
6-titrafluorophenyl acrylic acid ester, 2.
3, 4, 5. Examples include aromatic fluorine-containing (meth)acrylic esters such as 6-pentafluorophenyl methacrylic ester, and one type or a mixture of two or more of these can be used.

The usage amount of the polymerizable monomer (D) can be appropriately determined within the range of 60 to 98.45% by weight.

If the usage amount is less than 60% by weight or more than 98.45% by weight, the usage period of the polysiloxane (A), polymerizable silane compound (B) or unsaturated organic acid (C) is excessive or exceeds the above range. If the amount is too small, the above-mentioned drawbacks will occur, which is undesirable.

The polymers useful in the composition of the present invention include a polymerizable silane compound (B), an unsaturated organic acid (C), and others copolymerizable with these in the presence of the polysiloxane containing a terminal human oxygen group (A). It can be produced by polymerizing the polymerizable monoconcave body (D) by a conventionally known polymerization method. For example, solvents that can be used when employing the solution polymerization method include toluene, hexane, methyl ethyl ketone, ethyl cellosolve, ethyl acetate, isopropyl alcohol, etc. One type or a mixture of two or more of these can be used. You can. Examples of the polymerization initiator include common radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide.

The reaction temperature is room temperature to 200°C, preferably 40 to 120°C.
℃ range.

The polymer thus obtained can be used as it is as the surface-modifying composition of the present invention, but in consideration of workability during coating, it may be used after being dissolved or dispersed in various media. is preferred. In particular, a solvent solution of a polymer obtained by a solution polymerization method can be used as it is as the composition of the present invention with good workability. Further, when preparing the composition of the present invention, in addition to the polymer or a solution of the polymer, various additives such as a curing catalyst, inorganic or organic fine particles, and an antistatic agent which are commonly known may be added to the polymer or a solution thereof, which may impede the purpose of the present invention. There is no problem even if it is added within the above range.

(Effects of the Invention) The surface-modified composition of the present invention does not undergo layer separation even when left to stand, and the coating film obtained by applying it to a substrate has good adhesion to the substrate. In addition, it has good water repellency, slipperiness, and heat resistance.
It exhibits excellent surface properties such as migration resistance, and is used as a back coating agent for magnetic tapes, thermal printing materials, etc.
It exhibits excellent properties when applied to mm processing agents and the like.

The reason why the composition of the present invention exhibits such excellent properties is not yet clear, but it is thought to be as follows. That is, by polymerizing a monomer mixture containing a polymerizable silane compound (B) in the presence of a terminal hydroxyl group-containing polysiloxane (A), a polymer containing silane compound units is produced by polymerizing a monomer. The chains and polysiloxane are combined to obtain a polysiloxane graft polymer.

When the composition of the present invention containing such a graft polymer is applied to a substrate, the polysiloxane portion is oriented toward the air side and the polymer chain portion generated by polymerization is oriented toward the substrate side, resulting in water repellency. It is thought that this makes it possible to achieve both surface properties such as slipperiness and adhesion to the base material. However, this is not the only reason for any limitations.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way by these examples. In addition, all parts in the examples indicate parts by weight.

Reference Example 1 In a four-necked flask equipped with a thermometer, reflux condenser, dropping funnel, nitrogen inlet tube, and stirrer, dihydroxydimethylpolysiloxane of the formula (where n is 1500 on average) was prepared as a polysiloxane containing terminal hydroxyl groups. 30
10 parts of a wt% toluene solution and 100 parts of toluene were charged, and the temperature was raised to 80°C under a nitrogen atmosphere. To this, 64.4 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid, 5.6 parts of acrylic acid and droxyethyl,
20% by weight of a homogeneous monomer solution consisting of 5 parts of γ-methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added, and initial polymerization was carried out at 80° C. for 30 minutes. Next, the remaining monomer homogeneous solution was added dropwise over a period of 2 hours at the same temperature, and when the polymerization was continued for 20 minutes after the addition was completed, 100 parts of isopropyl alcohol was added to dilute the solution.

Subsequently, stirring was continued for 3 hours and 40 minutes while maintaining the temperature at 80°C to continue the polymerization reaction, and then the solution of the polymer for the surface modification composition of the present invention (hereinafter referred to as polymer solution (1)) was cooled. ) was obtained. The viscosity of the obtained polymer solution (1) was 5
The solid content was 33.3% by weight at 0 cps (25°C, B-type viscometer, 60rp+e).

Reference Example 2 Add Reference Example 1 to a four-bottle flask similar to that used in Reference Example 1.
33.3 parts of a 30% by weight toluene solution of the same terminal hydroxyl group-containing polysiloxane as used in the above and 100 parts of toluene were charged, and the temperature was raised to 80° C. under a nitrogen atmosphere. To this, 50 parts of methyl methacrylate, 20 parts of butyl acrylate, 20 parts of acrylonitrile, 5 parts of acrylic acid, γ
- Using a homogeneous monomer solution consisting of 5 parts of methacryloxypropyltrimethoxysilane and 2i1 azobisisobutyronitrile, the same initial polymerization operation and dropping operation of the homogeneous monomer solution as in Reference Example 1 were performed. After the completion of the dropwise addition of the monomer homogeneous solution, the mixture was continued for 30 minutes, and 100 parts of ethyl alcohol was added to dilute the solution. Further at 80℃ for 3 hours 3
After continuing the polymerization reaction for 0 minutes, the solution was cooled to obtain a solution of the polymer for surface modification composition of the present invention (hereinafter referred to as polymer solution (2)). The viscosity of the obtained polymer solution (2) was 70
The solid content was 33.0% by weight according to CDS (25° C., Model 8 packing meter, 60 ml).

Reference Example 3 Into a four-bottle flask similar to that used in Reference Example 1, 3 parts of dihydroxydimethylpolysiloxane represented by the formula (however, n is 650 on average) as a polysiloxane containing terminal hydroxyl groups and 100 parts of toluene were charged, and nitrogen was added. Under atmosphere, 80℃
The temperature rose to . A homogeneous monomer solution consisting of 30 parts of methyl methacrylate, 30 parts of styrene, 30 parts of vinyl acetate, 5 parts of acrylic acid, 5 parts of 2-styrylethyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added to this. The same initial polymerization operation and dropping operation of a homogeneous monomer solution as in Reference Example 1 were performed. 15 after finishing dropping monomer homogeneous solution
When polymerization was continued for minutes, isopropyl alcohol 100
diluted by adding 1 part. The polymerization reaction was further continued at 80° C. for 3 hours and 45 minutes, and then cooled to obtain a solution of the polymer for surface modification composition of the present invention (hereinafter referred to as polymer solution (3)).

) was obtained. The viscosity of the obtained polymer solution (3) was 55 cp
s (25°C, B-type viscometer, 60rE) m>, solid content 3
It was 3.9% by weight.

Reference Example 4 A comparative polymer solution (hereinafter referred to as a comparative polymer solution (1
). ) was obtained. Obtained comparative polymer solution (1)
When the mixture was allowed to stand overnight, a large amount of polysiloxane was separated into the upper layer.

Reference Example 5 The same terminal hydroxyl group as used in Reference Example 1 was added to 302 parts of a polymer solution obtained in exactly the same manner as in Reference Example 1, except that the terminal hydroxyl group-containing polysiloxane in Reference Example 1 was not used. Add 10 parts of the polysiloxane containing polysiloxane as a 30% by weight toluene solution and mix to form a comparative polymer solution (hereinafter referred to as comparative polymer solution (2)).

) was obtained. When the obtained comparative polymer solution (2) was allowed to stand, the polysiloxane gradually separated into an upper layer.

Examples 1 to 3 and Comparative Examples 1 to 2 Polymer solutions (1) to (3) obtained in Reference Examples 1 to 5 and comparative polymer solutions (1) to (2) were diluted with toluene, A polymer solution having a solid content of 25% by weight was prepared, and 4 parts of di-n-butyltin dilaurate was added to each 100 parts of the polymer solution to prepare the surface-modified composition (1) of the present invention.
- (3) and comparative surface modification compositions (1) - (2) were prepared.

The performance of these compositions was evaluated using the performance test method shown below. The evaluation results are shown in Table 1. In addition, regarding the slipperiness and water repellency, the measured values of the glass plate are also shown for reference.

1) The surface modification composition was applied to a thickness of 1.5μ on a slippery glass plate, dried at 100°C for 1 minute, and left overnight as a test piece to measure the coefficient of dynamic friction of the coating film. The slipperiness was evaluated by this.

The coefficient of dynamic friction was measured using a surface property measurement ta (manufactured by Shinto Kagakusha, model HE ID0N-14).

2) Water repellency: The same test piece as used in the slip test was used.

Measuring the contact angle of paint film with water Water repellency was evaluated by

The contact angle is measured using a contact angle measuring device (consonant interface). Using Kagakusha, CA-A type), liquid Measured by drop method.

3) Heat resistance: The surface modification composition was applied to a thickness of 1.5 μm on one side of a polyester film with a film thickness of 6 μm, dried at 100° C. for 1 minute, and left overnight. The other side was coated with hot-melt ink. The coated surface of the surface-modifying composition was placed on the image-receiving paper with the surface facing the thermal head, and thermal printing was performed using a commercially available Gl facsimile machine (Fujitsu, FACOM FAX6401540). The results were evaluated as follows: O: No stains on the thermal head; Printing clarity: X: Dirt was attached to the thermal head, printing was unclear.

4) Retention of physical properties of coating film: 15% of the surface modification composition was applied to high-quality paper.
The coating film was applied to a thickness of μ, dried at 130° C. for 10 minutes, and left to stand at room temperature for 2 hours. The resulting coating film was then pressure-bonded with adhesive tape (Tiban polyester tape). After storing this at 50° C. for 4 weeks, the adhesive tape was peeled off from the high-quality paper, and the peeled adhesive tape was pressure-bonded to a stainless steel plate to measure the residual adhesive strength of the adhesive tape.

In addition, the residual adhesive strength is determined by a 180 degree peel test. Expressed as peeling force by experiment, peeling rate was performed at 30aa for 1 minute.

Surface modification based on residual adhesive strength The retention of physical properties of the coating film can be evaluated. Ru. If the residual adhesive strength is large, the paint film 11 Peeling is less likely to occur, and coatings are The retention of sex is good. Also, the remaining If the adhesive force is small, the interlayer of the paint film Peeling (especially polysiloxane in the coating) (components may fall off) easily, resulting in damage to the paint film. The retention of physical properties is poor.

5) After allowing the stable two-surface modified composition to stand for 24 hours,
The state of layer separation was observed and evaluated as follows: Q: Uniform state x: State where the layers were separated into two layers.

Claims (1)

[Claims] 1. Terminal hydroxyl group-containing polysiloxane (A) 1-
In the presence of 20% by weight, 0.0% of polymerizable silane compound (B)
5 to 10% by weight, unsaturated organic acid (C) 0.5 to 10% by weight, and other polymerizable monomers (D) copolymerizable with these 6
0 to 98.45% by weight (however, (A), (B), (C)
The total of components (D) and (D) is 100% by weight. ) A surface modification composition comprising a polymer obtained by polymerizing.