JPH0234974B2 - - Google Patents

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, or steel plate to impart surface properties such as water repellency, slipperiness, heat resistance, and migration resistance. It is. (Prior art) In recent years, along with the development of electronic devices, the requirements for performance such as slipperiness, heat resistance, and abrasion resistance of magnetic tapes, floppy disks, thermal printing materials, etc. have become more and more 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 roughly divided into two types: modification of the film itself, which is used as a base material for magnetic tapes and thermal printing materials, and modification by applying a modifying substance to the surface. As for the former method, a method using a heat-resistant resin film such as polyimide or polysulfone as a base material has been disclosed (Japanese Patent Application Laid-open No. 152894/1989), but this method is expensive and does not require the use of thin films necessary for high functionality. It is difficult to obtain. In addition, for polyester film, which is the most commonly used base material, there is a method in which inorganic particles are generated during polyester production (Japanese Patent Publication No. 34-5144).
) or a method of adding inorganic particles such as silica or calcium carbonate (Special Publication No. 42-24099, Special Publication No. 24099,
No. 43-12013) etc. disclose a method of obtaining a film with good slipperiness, but these methods
It is difficult to control the particle size of the generated particles, and it is necessary to add a large amount of inorganic particles to obtain slipperiness, which reduces workability during film formation and causes problems in thinning and transparency of the film. be. Furthermore, a method of introducing a polysiloxane containing terminal hydroxyl groups into the polyester main chain (Japanese Patent Application Laid-Open No. 168027/1983)
is also 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 base material with silicone resin, epoxy resin, melamine resin, fluororesin, etc. to modify the surface (U.S. patent
No. 4310600, Special Publication No. 59-39308, Japanese Patent Publication No. 55-7467
No.) has been disclosed, but it has the drawback that the properties aimed at improving 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 (JP-A-58-154766, JP-A-58-154766;
No. 164656) has been disclosed, and 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 method, and
The present invention provides a composition that provides a surface that is slippery, heat resistant, and wear resistant. (Means and effects for solving the problem) The present inventors have effectively utilized polysiloxane which has excellent heat resistance, slipperiness, and migration resistance, and has achieved good adhesion to the base material. As a result of intensive research on the surface-modifying composition shown in Table 1, it was 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 terminal hydroxyl groups has been found to be suitable for use in films, fibers, etc. The present invention was completed based on the discovery that it has good adhesion to base materials such as steel plates, and exhibits excellent heat resistance, slipperiness, and migration resistance. That is, in the present invention, in the presence of 1 to 20% by weight of a terminal hydroxyl group-containing polysiloxane (A), 0.05 to 10% by weight of a polymerizable silane compound (B), and 0.5 to 0.5% by weight of an unsaturated organic acid (C).
10% by weight and 60 to 98.45% by weight of other polymerizable monomers (D) copolymerizable with these (however, (A), (B), (C) and
The total of component (D) shall be 100% by weight. ) 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 (However, R ¹ and R ² are each independently a hydrocarbon group that may be substituted with a monovalent halogen, and n is an integer of 1 or more.) Currently, various types are easily available. It is available and can be used for any purpose. The molecular weight of the polysiloxane (A) used is preferably one in which n is in the range of 1 to 2,000. n
If n is less than 10, the resulting 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 preferable. Furthermore, in addition to the polysiloxanes represented by the above general formula, polysiloxanes having partially branched side chains can also be used as the polysiloxane (A) without any problem. The amount of polysiloxane (A) containing terminal hydroxyl groups is 1 to 20% by weight, depending on the degree of surface modification.
It can be determined as appropriate within the range. If the amount used is less than 1% by weight, the surface properties will not be sufficient, and 20
If the amount exceeds % 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, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris. (β-methoxyethoxy)silane, allyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ - (meta)
acryloxypropylmethyldiethoxysilane,
γ-(meth)acryloxypropyltris (β-
methoxyethoxy)silane, 2-styrylethyltrimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)
Examples include ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, and one or two selected from these groups.
Mixtures of more than one species can be used. The amount of the polymerizable silane compound (B) to be used can be appropriately determined within the range of 0.05 to 10% by weight. In amounts less than 0.05% by weight, polysiloxanes (A), (B), and (C)
Since the bonding with the polymer consisting of component (D) is insufficient, 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 acid (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 organic acid (C) to be used can be appropriately determined 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 grafting reaction, and if the amount used exceeds 10% by weight,
This makes it difficult to balance the polymerization reaction and the grafting reaction, which impairs surface modification effects such as water repellency and slipperiness, and adhesion of the resulting composition. As the polymerizable monomer (D) used in the present invention,
For example, acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; methacrylic esters such as methyl methacrylate and butyl methacrylate; 2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid. (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxypropyl; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyls such as styrene and vinyltoluene; unsaturated nitriles such as acrylonitrile and methacrylonitrile ;
Unsaturated amides such as acrylamide and N-methylolacrylamide; α-olefins such as ethylene, propylene, and isobutylene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and t-butyl vinyl ether; vinylidene chloride, vinyl fluoride, vinylidene fluoride Halogen-containing α,β-unsaturated monomers such as trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H,
Fluorine-containing (meth)acrylic acid esters such as 2H, 2H-heptadecafluorodecyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate; 2,3,5,6-tetrafluorophenyl acrylic ester, 2 , 3,4,5,6-pentafluorophenyl methacrylate and other aromatic fluorine-containing (meth)acrylic esters, and it is possible to use one type or a mixture of two or more of these. can. The amount of polymerizable monomer (D) used is 60 to 98.45% by weight
It can be determined as appropriate within the range. If the amount used is less than 60% by weight or more than 98.45% by weight, the amount of the polysiloxane (A), polymerizable silin compound (B) or unsaturated organic acid (C) used will be more or less than the above range. This is not desirable because the above-mentioned drawbacks occur. The polymer useful in the composition of the present invention includes a polymerizable silane compound (B), an unsaturated organic acid (C), and other polymers copolymerizable with these in the presence of the terminal hydroxyl group-containing polysiloxane (A). It can be produced by polymerizing the monomer (D) using 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℃, preferably 40 to 120℃
℃ 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 exhibits excellent surface properties such as good water repellency, slipperiness, heat resistance, and migration resistance, and is suitable for magnetic tape,
It exhibits excellent properties when applied to back coating agents for thermal printing materials, fiber processing agents, etc. 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 polysiloxane containing a terminal hydroxyl group (A), a polymer chain containing silane compound units produced by polymerization of the monomer mixture is formed. 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 surface properties such as slipperiness and adhesion to the base material can be achieved at the same time. 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, prepare the formula as a polysiloxane containing terminal hydroxyl groups. (However, n is 1500 on average) 10 parts of a 30% by weight toluene solution of dihydroxydimethylpolysiloxane and 100 parts of toluene
The temperature was raised to 80°C under a nitrogen atmosphere. This was composed of 64.4 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid, 5.6 parts of 2-hydroxyethyl acrylate, 5 parts of γ-methacryloxypropyltrimethoxysilane, and 2 parts of azobisisobutyronitrile. 20% by weight of the homogeneous monomer solution was added and initial polymerization was carried out at 80°C for 30 minutes. Next, the remaining monomer homogeneous solution was added dropwise over 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. Continue to maintain the temperature at 80℃ for 3 hours.
After stirring for 40 minutes to continue the polymerization reaction, the solution was cooled to obtain a solution of the polymer for a surface-modifying composition of the present invention (hereinafter referred to as polymer solution (1)). The viscosity of the obtained polymer solution (1) was 50 cps (25°C, B type viscometer,
60 rpm), and the solid content was 33.3% by weight. Reference Example 2 A 30% by weight toluene solution of the same terminal hydroxyl group-containing polysiloxane as used in Reference Example 1 was placed in a four-necked flask similar to that used in Reference Example 1.
and 100 parts of toluene, under nitrogen atmosphere,
The temperature was raised to 80°C. Methyl methacrylate 50
parts, butyl acrylate 20 parts, acrylonitrile 20 parts
The same initial polymerization procedure as in Reference Example 1 was carried out and the monomer was A homogeneous solution was added dropwise. When the polymerization was continued for 30 minutes after the dropwise addition of the monomer homogeneous solution, 100 parts of ethyl alcohol was added to dilute the solution. The polymerization reaction was further continued at 80° C. for 3 hours and 30 minutes, and then cooled to obtain a solution of the polymer for the surface-modifying composition of the present invention (hereinafter referred to as polymer solution (2)). Obtained polymer solution (2)
The viscosity of is 70cps (25℃, B type viscometer, 60rpm),
The solid content was 33.0% by weight. Reference Example 3 In a four-necked flask similar to that used in Reference Example 1, a polysiloxane containing a terminal hydroxyl group was prepared using the formula (However, n is 650 on average) 3 parts of dihydroxydimethylpolysiloxane represented by the following formula and 100 parts of toluene were charged, and the temperature was raised to 80°C under a nitrogen atmosphere. In this, methyl methacrylate
Reference example 1 and A similar initial polymerization operation and dropping operation of a homogeneous monomer solution were performed. When the polymerization was continued for 15 minutes after the dropwise addition of the monomer homogeneous solution was completed, 100 parts of isopropyl alcohol was added to dilute the solution. The polymerization reaction was further continued at 80°C for 3 hours and 45 minutes, and then cooled to form a solution of the polymer for the surface-modifying composition of the present invention (hereinafter referred to as polymer solution (3)).
I got it. The viscosity of the obtained polymer solution (3) was 55 cps (25
℃, B-type viscometer, 60 rpm), solid content 33.9% by weight
It was hot. Reference Example 4 Reference Example 1 except that γ-methacryloxypropyltrimethoxysilane in Reference Example 1 was not used.
A comparative polymer solution (hereinafter referred to as
It is called comparative polymer solution (1). ) was obtained. When the obtained comparative polymer solution (1) was left overnight, a large amount of polysiloxane was separated into an upper layer. Reference Example 5 Reference Example 1 was added to 302 parts of a polymer solution obtained in exactly the same manner as Reference Example 1 except that the terminal hydroxyl group-containing polysiloxane in Reference Example 1 was not used.
Add 10 parts of the same terminal hydroxyl group-containing polysiloxane as used in 30% by weight toluene solution and mix well to obtain a comparative polymer solution (hereinafter referred to as comparative polymer solution (2)). Ta. When the obtained comparative polymer solution (2) was allowed to stand, the polysiloxane gradually separated into an upper layer. Reference Example 6 To produce an organoalkoxysilane condensate, the following components were placed in a reaction vessel. Part by weight γ-methacryloxypropyltrimethoxysilane
16.0 Organopolysiloxane 314.0 Xylene 78.0 The organopolysiloxane used here had the following properties. Total solid content (%) 100.0 Hydroxyl group content (%) 1.7 Average molecular weight Approximately 2000 This mixture was distilled to 130% while removing water by azeotropic distillation.
Condensation was achieved by refluxing for 30 minutes at <RTIgt;C,</RTI> then the next material was added. Part by weight N-butoxymethylacrylamide 222.0 Methacrylic acid 25.0 Acrylonitrile 200.0 Styrene 250.0 Butyl acrylate 425.0 Butanol 405.0 Xylene 327.0 Tertiaryidodecyl mercaptan 27.5 T-Butylperoxyisopropyl carbonate (high boiling point of 187°C to 205°C) hydrocarbon aromatic solvent
20 parts solution) 2.5 Reflux this mixture at 90-100°C for 4 hours, and then
0.64 parts of catalyst was added. Continue refluxing for another 2 hours,
Next, 210 parts of butanol, 0.64 parts of catalyst, and 265 parts of a high-boiling aromatic hydrocarbon solvent were added. Azeotropic reflux was then carried out for 7 hours, with 0.64 parts of catalyst added each hour except for the last 2 hours. The resulting mixture had a solids content of 48.5%. This is designated as comparative polymer solution (3). 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 with a solid content of 25% by weight,
To 100 parts of this material, 4 parts of di-n-butyltin dilaurate was added, and surface modification compositions (1) to (3) of the present invention and comparative surface modification compositions (1) to ( 2)
was 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. Comparative Example 3 The coating film of the comparative polymer solution (3) obtained in Reference Example 6 had a dynamic friction coefficient of 0.085. (1) Slip property: 1.5μ of the surface-modified composition is applied on the glass plate.
The slip properties were evaluated by measuring the coefficient of dynamic friction of the coating film using test pieces that were coated to a thickness of 100° C., dried for 1 minute at 100° C., and left overnight.
The coefficient of dynamic friction is measured using a surface property measuring device (manufactured by Shinto Kagakusha,
HEIDON-14 type). (2) Water repellency: The same test piece as used in the slip test was used. Water repellency was evaluated by measuring the contact angle of the coating film with water. The contact angle was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., model CA-A).
Measured by droplet method. (3) Heat resistance: A surface modification composition is applied to one side of a 6μ thick polyester film to a thickness of 1.5μ,
After drying at 100°C for 1 minute, it was left to stand overnight, and the other side was coated with hot-melt ink. Place the surface-modifying composition on the image-receiving paper with the surface to which it has been applied facing the thermal head, and place it on a commercially available G facsimile (manufactured by Fujitsu,
Using thermal printing through FACOM FAX640/540), we observed the state of dirt on the thermal head of the printing machine (statting resistance) and the clarity of the print. ○: No dirt on the thermal head, clear printing. Evaluation was made based on the fact that dirt was attached and the printing was unclear. (4) Retention of physical properties of coating film: The surface modification composition was applied to a thickness of 15μ on high-quality paper, and after drying at 130℃ for 10 minutes,
Adhesive tape (Nichiban Polyester Tape) was pressure-bonded to the coating film obtained by allowing it to stand at room temperature for 2 hours.
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 pressed onto a stainless steel plate to measure the residual adhesive strength of the adhesive tape. The residual adhesive strength was expressed as the peeling force determined by a 180 degree peel test, and the peeling speed was 30 cm/min. The ability of the surface-modifying composition to maintain the physical properties of the coating film can be evaluated based on the magnitude of the residual adhesive strength. When the residual adhesive strength is large, delamination of the coating film is less likely to occur, and the physical properties of the coating film are maintained well. In addition, when the residual adhesive strength is small, delamination of the coating film (particularly, shedding of the polysiloxane component in the coating film) easily occurs, and the retention of the physical properties of the coating film is poor. (5) Stability: After the surface-modified composition was allowed to stand for 24 hours, the state of layer separation was observed and evaluated: ○: uniform state; ×: state separated into two layers. 【table】

Claims (1)

[Claims] 1 Polysiloxane containing terminal hydroxyl group (A) 1
In the presence of ~20% by weight, 0.05% of polymerizable silane compound (B)
~10% by weight, unsaturated organic acid (C) 0.5~10% by weight, and other polymerizable monomers copolymerizable with these (D) 60~
A surface modification composition comprising a polymer obtained by polymerizing 98.45% by weight (however, the total of components (A), (B), (C) and (D) is 100% by weight).