JP3172466B2 - Sizing agent for glass fiber and glass fiber coated with it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sizing agent for glass fibers (hereinafter referred to as a sizing agent) used for sizing a large number of glass fibers, glass fibers coated with the sizing agent, and glass fibers. It relates to a coated one. More specifically, glass fibers used for reinforcing rubber products, particularly hydrogenated nitrile rubber (hereinafter, referred to as H-NBR), sizing agents used for producing the same,
And a coating of the glass fiber.

[0002]

2. Description of the Related Art In order to improve the strength and durability of rubber products such as rubber belts and rubber tires, it is widely practiced to embed glass fiber or the like as a reinforcing material in rubber products.

[0003] However, since glass fibers generally have poor affinity with rubber, if they are embedded in rubber as it is,
Does not adhere to rubber, or easily peels off even if adhered.
In this case, the glass fiber cannot satisfy the performance required as a reinforcing material for a rubber product.

[0004] Therefore, it is necessary to apply some treatment to the glass fiber so that the adhesion to the rubber is enhanced. Among various treatment methods, a surface treatment in which a treatment agent is applied to the surface of glass fiber and a coating film is formed thereon is currently widely performed.

For example, an invention in which glass fibers are produced using a sizing agent and a coating film of a component close to that of a rubber product is laminated three times on the glass fiber is disclosed in Japanese Patent Publication No. 5-71710.
No., published in Japanese Unexamined Patent Publication No. Further, an invention in which a glass fiber coated with a sizing agent containing an aminosilane and a modified styrene / butadiene latex (hereinafter, referred to as modified SBR) is coated with a resorcinol-formaldehyde condensate (hereinafter, referred to as RFL) is disclosed in Japanese Patent Application Publication No. H10-183,197. -65454.

[0006] There are a wide variety of types of rubber products currently on the market, and the properties of rubber are different for each type. Therefore, in order to optimize the adhesion between the rubber and the reinforcing material, it is necessary to change the coating material depending on the combination thereof.

[0007] Among rubber products, those using H-NBR as a raw material exhibit higher heat resistance than chloroprene rubber and butadiene rubber conventionally used generally. Therefore, a rubber product using H-NBR as a raw material can be used in a new field which could not be used in a conventional rubber product, or as a substitute having higher performance than a conventional product.

For example, when H-NBR is used as the material for the timing belt of the engine, the timing belt has high heat resistance and can be brought closer to the engine body. As a result, the size of the engine itself can be reduced.

[0009] Rubber products made from H-NBR (hereinafter, referred to as H-NBR)
When glass fiber is used as a reinforcing material for H-NBR products, a silane coupling agent and styrene-butadiene latex (hereinafter, referred to as SBR) are contained in several hundred ultrafine glass fibers. A glass fiber is manufactured by applying a sizing agent, and H-NB is further formed on the glass fiber.
A coating film containing R and RFL was formed in multiple layers (Japanese Patent Publication No. 5-71710).

[0010]

However, when a glass fiber using a sizing agent containing a silane coupling agent and a modified SBR or SBR is used as a reinforcing material for an H-NBR product, the glass fiber becomes a reinforcing material. Function could not be fully exhibited. That is, this glass fiber has poor adhesion to the H-NBR product, and cannot improve the bending fatigue property. This is because the modified SBR or the compatibility between SBR and H-NBR is poor, so that a sufficient adhesive force cannot be obtained at the interface.

The present invention has been made by focusing on the problems existing in the above prior art. An object of the present invention is to provide a glass fiber having high adhesiveness to H-NBR when glass fiber is used as a reinforcing material for an H-NBR product, and a sizing agent for producing the glass fiber.

[0012]

In order to achieve the above object, the sizing agent according to the first aspect of the present invention contains aminosilane and H-NBR.

[0013] The sizing agent according to the second aspect of the present invention is the sizing agent according to the first aspect, wherein the aminosilane is 0.1 to 0.1%.
2% by weight and 1 to 10% by weight of the H-NBR.

[0014] The sizing agent according to the third aspect of the present invention further comprises at least one selected from the group consisting of a rubber latex, an oil agent and an anti-aging agent in the first or second aspect of the present invention. Things.

The glass fiber of the invention described in claim 4 is the glass fiber coated with the sizing agent of any one of claims 1 to 3. The glass fiber of the invention according to claim 5 is obtained by adding H-N to the glass fiber of the invention according to claim 4.
A coating film containing BR and RFL is formed.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. This glass fiber is subjected to a surface treatment in order to sufficiently exhibit a function as a reinforcing material of the H-NBR product. This surface treatment refers to applying a sizing agent to bundle a large number of ultrafine glass fibers into one glass fiber.
Further, it refers to forming a protective film containing H-NBR and RFL on the glass fiber.

The sizing agent comprises aminosilane and H-NBR.
However, it is usually used by being mixed with a solvent.
This solvent is usually water, but may be any other chemically stable one. The sizing agent is applied to ultrafine glass fibers, and tens to hundreds of the ultrafine glass fibers are bonded to each other. Then, these ultrafine glass fibers are formed into one glass fiber.

Here, the ultrafine glass fiber refers to a fibrous glass having a diameter of about 10 μm drawn by a winding roller or the like from a nozzle attached to a lower part of a glass melting furnace. Further, the glass fiber referred to in the present invention includes both the ultrafine glass fiber and the glass fiber in which it is bundled.

The type of the glass fiber is not particularly limited, but E-glass (alkali-free glass) is preferable in terms of production cost, wide range of uses, and the like. Other types include high-strength glass. High-strength glass has a higher tensile strength than E-glass, and is effective when higher strength is required.

Aminosilane is a component contained in the sizing agent, and has a property of improving the compatibility between glass fiber as an inorganic substance and H-NBR as an organic substance. The type of the aminosilane is not particularly limited, but γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, δ-aminobutyltriethoxysilane, bis- (γ-aminopropyl) dimethoxysilane, δ-amino Butylethyldimethoxysilane, γ-aminoallyltrimethoxysilane, β-aminovinyltriethoxysilane, ε-aminocyclohexylethyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, p-amino Phenyltriethoxysilane is preferred.

H-NBR is a highly saturated polymer having a nitrile group. These types are not particularly limited, but include those obtained by hydrogenating a copolymer of unsaturated nitrile and ethylene, those obtained by hydrogenating a copolymer of unsaturated nitrile and conjugated diene, and those of unsaturated nitrile, ethylene and conjugated diene. What hydrogenated the original copolymer etc. are mentioned.

Specific examples of these H-NBRs include butadiene-acrylonitrile copolymer rubber, isoprene-butadiene-acrylonitrile copolymer rubber, isoprene-
Acrylonitrile copolymer rubber, butadiene / methyl acrylate / acrylonitrile copolymer rubber, butadiene /
Acrylic acid / acrylonitrile copolymer rubber, butadiene / ethylene / acrylonitrile copolymer rubber, butyl acrylate / ethoxyethyl acrylate / vinyl chloroacetate / acrylonitrile copolymer rubber, or butyl acrylate / ethoxyethyl acrylate / vinyl norbornene / acrylonitrile copolymer rubber And hydrogenated ones.

The H-NBR preferably has an iodine value of 120 or less, more preferably 0 to 100. This iodine value is measured according to JIS K0070. H that meets this requirement
Specific examples of -NBR include Zetpol latex (trade name, manufactured by Zeon Corporation).

The content of aminosilane in the sizing agent is as follows:
Preferably it is in the range of 0.1 to 2% by weight. Further, the content is preferably in the range of 0.2 to 0.5% by weight. When the content is less than 0.1% by weight, aminosilane cannot be uniformly present on the entire surface of the glass fiber, so that the convergence of the glass fiber is reduced, and as a result, the glass fiber is not united. Conversely, if the content exceeds 2% by weight, the amount of aminosilane adhering to the glass fiber surface does not change, so that it is not necessary to include more.

The content of H-NBR in this sizing agent is 1
It is preferably in the range of 10 to 10% by weight. And 2
Preferably, it is in the range of ５5% by weight. If the content is less than 1% by weight, the content of H-NBR is too small, so that H-NBR cannot be present on the entire surface of the glass fiber. In this case, the glass fiber has poor adhesion to the H-NBR product. Further, since the adhesion between the glass fibers is weak, the fibers rub against each other at the time of winding, and fluff is generated. Conversely, if the content is more than 10% by weight, the adhesion between the glass fiber and the rubber product does not improve, so that it is not necessary to contain more.

This sizing agent comprises aminosilane and H-NBR
In addition, it may contain at least one selected from the group consisting of rubber latex, oil agent and antioxidant. When the rubber latex is contained in the sizing agent, the sizing agent is uniformly present on the glass fibers, so that the glass fibers are uniformly uniformly bunched. In addition, the glass fiber is less likely to fluff during a winding process or the like.

The type of the rubber latex is not particularly limited, but includes butadiene / styrene copolymer latex, dicarboxylated butadiene / styrene copolymer latex, vinylpyridine / butadiene / styrene terpolymer latex, chloroprene latex, butadiene latex, Chlorosulfonated polyethylene latex or acrylonitrile-butadiene copolymer latex is preferred.

The oil agent imparts lubricity to the glass fiber by being included in the sizing agent, so that fluffing during the winding process can be suppressed. The type of the oil agent is not particularly limited, but may be an aliphatic hydrocarbon such as paraffin wax, or a saturated or unsaturated higher monocarboxylic acid, dicarboxylic acid, or oxycarboxylic acid, and a monohydric lower alcohol such as butanol or ethylene. Higher fatty acid esters in combination with polyhydric alcohols such as glycol, glycerin, pentaerythritol or sorbitol, and also polyoxyethylene such as polyoxyethylene nonylphenyl ether and polyoxyethylene alkylphenyl ether such as polyoxyethylene lauryl ether Surfactants such as alkyl ethers or polyoxyethylene fatty acid esters such as polyoxyethylene lauryl ester are preferred.

The antioxidant, when contained in a small amount in the sizing agent, can prevent the sizing agent from being deteriorated by oxidation or heat. The type of this anti-aging agent is
Although not particularly limited, p-phenylenediamine derivatives such as N, N′-diphenyl-p-phenylenediamine,
Ketone / amine condensates such as 2,2,4-trimethyl-1,3-dihydroquinone, naphthylamines such as N-phenyl-1-naphthylamine, diphenylamine derivatives such as octylated diphenylamine, 2,6-di-t
Monophenols such as -butyl-4-methylphenol and bisphenols such as 2,2'-methylenebis (4-methyl-6-t-butylphenol) are preferred.

In the glass fiber, the amount of the sizing agent to be attached is preferably 0.1 to 2% by weight.
More preferably, it is 2 to 0.5% by weight. If the amount of adhesion is less than 0.1% by weight, the amount of the sizing agent with respect to the glass fiber is too small, and fuzz is generated in a winding operation by a machine or the like, and the strength of the glass fiber is reduced. Conversely, if the amount of the sizing agent adhered to the glass fiber is more than 2% by weight, the film formed by the sizing agent becomes too thick. In this case, additional HN on the glass fiber
When a coating film containing BR and RFL (hereinafter, referred to as a coating film) is formed, it becomes difficult for the treating agent to enter the inside of the glass fiber. Accordingly, in this case, the interface between the sizing agent and the coating film is apt to occur.

Further, glass fibers include H-NBR and R
It is preferable to form a coating film containing FL. By forming this coating film, the surface of the glass fiber is protected and fixed to the inside. Therefore,
This glass fiber becomes strong in friction during the winding or twisting process, and is easily handled thereafter. In addition, since the coating film contains N-NBR, the adhesiveness to the H-NBR product does not deteriorate.

The method of applying the sizing agent to the glass fibers is not particularly limited, but the step of drawing the glass in a molten state from a number of nozzles provided in the lower part of the melting furnace into a fibrous form with a take-up roller or the like involves applying an applicator. Is generally used. Here, the applicator is
This device includes a roller belt and a sizing agent tank. A part of the roller belt contacts the sizing agent while rotating, so that the surface of the roller belt is constantly wet with the sizing agent. Then, the sizing agent is transferred to the ultrafine glass fibers by bringing the ultrafine glass fibers into contact with the roller belt.

The method of forming the coating film on the glass fiber is not particularly limited. However, when several glass fibers are aligned and twisted into a thick glass fiber, a treatment agent for the coating film is used. A method of impregnating the thick glass fiber into a tank containing the same is general.

The above-mentioned thick glass fiber can be further coated on its surface with a halogen-containing polymer and an isocyanate compound. By further applying this coating, the adhesiveness with the H-NBR product can be further improved.

[0035]

EXAMPLES Example 1 0.5% by weight of aminosilane (γ-aminopropyltriethoxysilane) in pure water, H-NBR (Z
etpol: manufactured by Zeon Corporation, solid content 40% by weight)
% By weight and 0.1% by weight of an alkylphenol ether were used as a sizing agent. The components of this sizing agent are shown in Table 1 below.

Further, the melted E-glass was formed into ultra-fine glass fibers having a diameter of 9 μm, and the sizing agent was applied to the ultra-fine glass fibers using an applicator. One hundred glass fibers were bundled into 200 glass fibers. The amount of the sizing agent attached to the glass fiber was 0.4% by weight with water removed.

[0037] Three of these glass fibers are aligned and H-N
BR is immersed in a treating agent (hereinafter referred to as coating agent) consisting of 60% by weight, RFL at 35% by weight, 25% ammonia water at 1% by weight and pure water at 4% by weight, and immediately dried by heating to form a coating film. Was formed. This glass fiber had its surface completely covered with a coating film. The components of this coating are set forth in Table 2 below. The units of numerical values shown in Tables 1 and 2 below are% by weight.

The glass fiber on which the coating film was formed was twisted 8 times / 10 cm, twisted 11 more times, and twisted 8 times / 10 cm in the opposite direction to the twist, and the following test was performed. Glass fiber was obtained. (Tensile strength test) Glass fiber and H-NB for this test
In order to test the adhesiveness with the R product, the glass fiber was placed on a test piece (25 mm × 12 mm) shown in Table 3 below, and was vulcanized at 150 ° C. for 30 minutes and bonded. The test piece was pulled in the fiber direction by a tensile tester, and the resistance when the test piece was disconnected was measured. This test was designated as Test 1, and the results are shown in Table 4 below. Table 4 also shows the state of the test piece at the disconnection point in Test 1. (Test of Adhesive Strength Retention) The glass fiber for this test was embedded in rubber having the same components as the above-mentioned test piece, and the width was 19 mm.
The belt was processed into a 980 mm long toothed belt. The toothed belt was put on a tensile tester and its initial strength was measured. Then, the toothed belt is heated at 120 ° C. and 6,000 rpm.
The test was conducted for 600 hours in an environment of m. After the running test, the toothed belt was set on a tensile tester, the tensile strength was compared with the initial strength, and the adhesive strength retention was calculated. This test was designated as Test 2, and the results are shown in Table 4 below. (Example 2) The components of the sizing agent and the coating agent described in Example 1 were changed to the components shown in Tables 1 and 2 below.
Otherwise, the test was performed under the same conditions as in Example 1. Comparative Example 1 The components of the sizing agent described in Example 1 were changed to the components shown in Table 1 below. Otherwise, the test was performed under the same conditions as in Example 1. In addition, the partial peeling of Table 4 means
This refers to a state in which the glass fibers are partially visible from the disconnected part of the test piece. Therefore, the glass fiber has undergone interfacial delamination with a part of the test piece. Comparative Example 2 The components of the sizing agent described in Example 1 were changed to the components shown in Table 1 below, and the components of the coating agent were changed to the components shown in Table 2 below. Otherwise, the test was performed under the same conditions as in Example 1.

[0039]

[Table 1]

(Unit: wt%) (* 1) γ-aminopropyltriethoxysilane (* 2) H-NBR latex (manufactured by Zeon Corporation, solid content: 40 wt%) (* 3) Carboxylated styrene / butadiene Polymerized latex (manufactured by Nippon Zeon, solid content 40% by weight) (* 4) Vinyl pyridine / styrene / butadiene terpolymer latex (manufactured by Zeon Corporation, solid content 40% by weight) (* 5) Chlorosulfonated polyethylene latex (Sumitomo) (Chemical company, solid content 40% by weight)

[0041]

[Table 2]

(Unit: weight%) (* 6) Resorcin / formaldehyde condensate (resorcin / formaldehyde = 1 / 1.5: weight ratio, solid content 8% by weight)

[0043]

[Table 3]

[0044]

[Table 4]

In the tensile test of Test 1, Example 1
The test piece of Example 2 was broken while the glass fiber and the test piece were adhered. Comparative example 1
In the test piece of No. 1, the glass fiber partially protruded from the fracture surface. Further, in the test piece of Comparative Example 2, the glass fiber completely protruded from the cut surface. The glass fibers that protruded from the cut surface were generated due to the occurrence of interfacial separation at the bonding surface between the sizing agent and the coating film.

From the above, glass fiber and H-NBR
It was found that when a layer containing no H-NBR was present between the product and the product, the adhesive strength was low, and interface peeling was liable to occur therefrom.

[0047]

The present invention is configured as described above, and has the following effects. According to the sizing agent according to the first aspect of the present invention, by containing aminosilane and H-NBR together in the sizing agent, glass fibers and H-N
Adhesion with BR products can be improved.

According to the sizing agent of the second aspect,
In addition to the effects of claim 1, aminosilane and H-NB
Since R and R can exist uniformly in the entire glass fiber, H-N
Adhesion with BR products can be further improved.

According to the sizing agent of the third aspect,
In addition to the effects described in claim 1 or claim 2, a new function such as improvement in adhesion between glass fibers or prevention of denaturation of the sizing agent by containing rubber latex, oil agent or anti-aging agent in the sizing agent. Can be added to the sizing agent.

According to the glass fiber of the fourth aspect of the present invention, a glass fiber having good adhesiveness to an H-NBR product is obtained by using the sizing agent according to any one of the first to third aspects. be able to.

According to the glass fiber of the invention described in claim 5, in addition to the effect described in claim 4, the handling of the glass fiber is facilitated by forming a coating film on the surface thereof. As a result, it is possible to prevent the generation of fluff of the glass fiber during the winding process or the like, and to maintain the strength of the glass fiber itself at a high level.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 25/10 D06M 13/513 D06M 15/693 C08J 5/08

Claims (5)

(57) [Claims] 1. A sizing agent for glass fibers containing an aminosilane and a hydrogenated nitrile rubber. 2. The content of the aminosilane is 0.1 to 2
The sizing agent for glass fibers according to claim 1, wherein the content of the hydrogenated nitrile rubber is 1 to 10% by weight. 3. The sizing agent for glass fibers according to claim 1, further comprising at least one selected from the group consisting of a rubber latex, an oil agent and an antioxidant. 4. A glass fiber to which the sizing agent for glass fiber according to claim 1 is applied. 5. The glass fiber according to claim 4, wherein a coating film containing a hydrogenated nitrile rubber and a resorcinol-formaldehyde condensate is formed.