KR970007319B1 - Laminated glass product and process for its production - Google Patents

Abstract

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Description

Laminated Glass Articles and Methods for Making the Same

1 is a cross-sectional view of a cathode ray tube having glass bonded to the front surface;

2 shows the spraying method of the adhesive for producing cathode ray tubes;

3 shows the way of curing the adhesive;

4 shows a method for measuring the amount of charged voltage in the examples and comparative examples of the present invention.

* Explanation of symbols for main parts of the drawings

1: main body of cathode ray tube 2: windshield

3: adhesive layer 4: adhesive tape for sealing

5: adhesive injection inlet 6: ultraviolet lamp

7 sensor 8 recorder

9: ground wire

The present invention relates to a photocurable resin composition for glass lamination having excellent antistatic property, flexibility, and transparency, a laminated glass article having a cured product of the photocurable resin composition as an inner layer, and a method of manufacturing the same.

For the production of laminated glass, it is known to bond glass to glass using an organic polymer film such as polyvinylbutyral. However, when using such an adhesive, a complicated time-consuming process is required for lamination.

In order to improve the overall process, extensive research has been conducted to develop liquid resins for glass lamination, and some of these liquid resins are substantially in use.

Such resins may be mentioned epoxy resins, unsaturated polyester resins, polyurethane resins and silicone resins.

However, these resins usually require heat curing, and it usually takes a long time to cure them at room temperature. Therefore, they have the disadvantage of low productivity.

Several photocurable resins have been known to overcome this drawback. Representative examples include acrylate type photocurable resins, epoxy type photocurable resins, and N / thiol type photocurable resins. All of these have characteristics that can be cured at room temperature within a short time by irradiation with ultraviolet or visible light.

Among them, epoxy type photocurable resins are not suitable for glass lamination because their cured products are usually very hard, lack flexibility, and are not suitable for transparency.

Regarding the acrylate type photocurable resin, Japanese Patent Laid-Open Publication No. 48777/1974 discloses a composition containing a urethane-modified poly (meth) acrylate as a main component, and Japanese Patent Laid-Open Publication No. 8856/1977 Japanese Patent Laid-Open Publication No. 166573/1984 discloses a composition containing polyether mono (meth) acrylate as a main component in Japanese Patent Laid-Open Publication No. 166573/1984, which discloses a composition containing butadiene-modified poly (meth) acrylate as a main component. It is. Among these acrylate photocurable resins, those containing polyacrylate as a main component tend to crosslink during the polymerization reaction, so that it is difficult to obtain a flexible purification product. Therefore, for glass lamination, compositions containing monoacrylate as the main component are used (US Pat. No. 4,599,274).

N / thiol type photocurable resins mainly consist of polyenes and polythiols. They are less susceptible to hardening impairments by air, so that the equivalent ratio of carbon-carbon unsaturated bonds (hereinafter referred to as C = C) of the polyene to the mercapto group (hereinafter referred to as -SH) of the polythiol used in the composition. Or by changing the number of functional groups of the polyene or polythiol, the cured product having various hardness can be obtained (Japanese Patent Laid-Open Nos. 3269/1972 and 162798/1979).

Recently, however, the resin for glass lamination used for laminating non-reflective glass on a display surface of a cathode ray tube has an antistatic property in order to prevent various failures due to static electricity such as adhesion of dust or electric shock. Or more specifically, it is required to have a volume resistivity of less than 5 × 10 ⁹ Ω · cm. However, conventional photocurable resins lack antistatic property. Therefore, in order to prevent the various failures caused by the above-mentioned static electricity, cumbersome and uneconomical methods such as a method of forming a conductive coating film on the surface of the non-reflective glass have been commonly used.

Therefore, it is an object of the present invention to provide a photocurable resin composition in which the cured product has excellent transparency and flexibility, and excellent antistatic properties of less than 5 × 10 ⁹ Ω · cm in volume resistivity.

Another object of the present invention is to provide a laminated glass article having a cured product of the photocurable resin composition and a method for producing the same as an inner layer for preventing an antistatic obstacle.

It has been found that these objects can be achieved by using as a main component a radically polymerizable monomer having a specific chemical structure.

The present invention mainly consists of a radically polymerizable monomer having two or more ethylene oxide repeat units in a molecule and a photopolymerization initiator, and the cured product has a volume resistivity of less than 5 × 10 ⁹ Ω · cm. To provide.

The present invention also provides a laminated glass article having, as an inner layer, a photocurable resin whose cured product exhibits a volume resistivity of less than 5 × 10 ⁹ Ω · cm.

The present invention also provides a method for producing a laminated glass article comprising bonding a plurality of glass sheets using a photocurable resin in which the cured product has a volume resistivity of less than 5 × 10 ⁹ Ω · cm.

Next, the present invention will be described in detail with reference to preferred embodiments.

The photocurable resin composition of the present invention contains a radically polymerizable monomer having two or more, preferably four or more ethylene oxide (-CH ₂ -CH ₂ -O-) repeating units in the molecule. Particularly preferred specific examples thereof include (A) acrylate compositions and (B) polyene / polythiol compositions as listed below.

Acrylate Composition (A)

Photocurable resin composition mainly consisting of the following components (1) and (2):

(1) An acrylate or methacrylate of the general formula (I) having an average molecular weight of about 500 to 5,000:

Wherein X and Y are each acryloyl group, methacryloyl group, hydrogen atom, halogen atom, alkyl group, or substituted phenyl group or unsubstituted phenyl group, and R ₁ is an aliphatic divalent hydrocarbon having 3 or more carbon atoms Or an aromatic divalent hydrocarbon group, n ₁ is an integer of 2 or more, and n ₂ is an integer of 1 or more, provided that at least one of X and Y is an acryloyl group or a methacryloyl group.

(2) photopolymerization reaction initiator

Polyene / Polythiol Composition (B)

Consisting mainly of polyenes, polythiols and photopolymerization reaction initiators, all or part of the polyenes are polyether poly (meth) allyl ethers and / or polyether poly (meth) acryl having two or more ethylene oxide repeat units in the molecule Photocurable resin composition which is a rate.

As monomers that can be used in the acrylate composition (A), for example, a block copolymer of ethylene oxide and propylene oxide, or a copolymer of glycol mono (meth) acrylate, ethylene oxide and tetrahydrofuran made of a random copolymer Glycol mono (meth) acrylates made of copolymers and mono (meth) s having hydrogen in the terminal hydroxyl groups of said mono (meth) acrylates substituted with halogen atoms, alkyl groups, or substituted phenyl groups or unsubstituted phenyl groups Acrylates. Such monomers may be used alone or in combination of two or more mixtures. The monomer of the said acrylate composition (A) is not limited to the said specific example.

When the average molecular weight of such an acrylate is less than 500, there may be a problem in that curing shrinkage is present and the flexibility and antistatic property of the cured product are not suitable. On the other hand, when the average molecular weight exceeds about 5,000, such monomers are difficult to prepare. Polyethylene glycol mono (meth) acrylates that are liquid at room temperature are excluded from component (1) of the present invention because they have a low molecular weight and become like wax at room temperature even if the average molecular weight is 500 or more.

Moreover, radically polymerizable monomers other than the acrylate of the component (1) of this invention can also be added if it does not adversely affect the objective of this invention. Such additional monomers include, for example, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, phenoxyalkyl (meth) acrylates, glycidyl (meth) acrylates, tetrahydrofurfuryl (meth ) Various mono acrylates such as acrylate, urethane mono (meth) acrylate and dicyclopentadienyloxyethyl (meth) acrylate, and polyether di (meth) acrylate, epoxy poly (meth) acrylate, poly Poly (meth) acrylates such as urethane poly (meth) acrylates, butadiene-modified poly (meth) acrylates and trimethylolpropane tri (meth) acrylates.

Regarding the monomers that can be used in the polyene / polythiol type composition (B), the polyene may be, for example, polyethylene glycol di (meth) allyl ether or di (meth) acrylate; Glycol di (meth) allyl ether or di (meth) acrylate made of a block copolymer or a random copolymer of ethylene oxide and propylene oxide; Glycol di (meth) allyl ether or di (meth) acrylate made of a block copolymer or a random copolymer of ethylene oxide and tetrahydrofuran; Polyethylene glycol diglycidyl ether di (meth) acrylate; Or polyol poly (meth) allyl ether or poly (meth) acrylate obtained by adding 2 moles or more of ethylene oxide to 1 mole of a polyhydric alcohol such as bisphenol A, glycerol, trimethylolpropane or pentaerythritol. In each case, those having two or more, preferably four ethylene oxide (CH ₂ CH ₂ O-) repeat units in the molecule are used. If a monomer having no or one ethylene oxide repeat unit is used as the main component, the volume resistivity of the cured product will be high, and the antistatic property will be inadequate.

In the polyene / polythiol type composition of the present invention, the polyene preferably contains compounds of the following general formulas (II) and / or (III):

Wherein R ₂ , R ₄ , R ₅ and R ₇ are each a hydrogen atom or a methyl group, R ₃ and R ₆ are each an aliphatic or aromatic divalent hydrocarbon group, n ₃ and n ₅ are each an integer of 2 or more; , n ₄ and n ₆ are each an integer of 0 or 1 or more.

The polyene / polythiol type composition of the present invention contains the polyene as a basic component. In addition to the polyenes, other polyenes may be added as long as the object of the present invention (antistatic properties, transparency, flexibility, elasticity, etc.) is not impaired. Such further polyenes include, for example, divinylbenzene, diallyl phthalate, diallyl malate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerol diallyl ether, (poly Propylene glycol diallyl ether, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Various epoxy acrylates, urethane acrylates and polyester acrylates. However, additional polyenes are not limited to the above specific examples.

Typical examples of polythiols that may be used in the present invention include diglycol dimercaptan, triglycol dimercaptan, tetraglycol dimercaptan, thiodiglycol dimercaptan, thiotriglycol dimercaptan, thiotetraglycol dimercaptan , Tris- (mercaptopropyl) isocyanurate, (poly) ethylene glycol dimercapto propionate, (poly) propylene glycol dimercapto propionate, tris- (2-hydroxyethyl) isocyanurate -Tris-β-mercapto propionate, polythiols sold under the trade name DION3-800L (manufactured by Diamond Shamrock Company), and polythiol prepolymers obtainable by reacting these polythiols with polyepoxides. The amount of polyene and polythiol used in the composition of the present invention is such that the equivalent ratio of C = C of polyene to -SH of polythiol is usually 1.5: 1 to 1: 1.5, preferably 1.2: 1 to 1: 1.2, more Preferably it is about the grade which will be in the range of about 1: 1. If the amount of polyene and polythiol is out of the above range, there may be a problem that the cured product exhibits odor, the hardness is too low, and in the extreme case, the composition is hardly cured.

Specific examples of the photopolymerization initiators used in the compositions of the present invention are illustrated below, but these initiators are not limited to the specific examples in all cases of (A) and (B) above. That is, as the photopolymerization initiator, for example, benzoin and its derivatives, benzyl and its derivatives, benzophenone and its derivatives, anthraquinone and its derivatives, acetophenone and its derivatives, diphenyldisulfide, thioxanthone and its derivatives There is. The initiator is preferably used in an amount in the range of 0.01 to 5 parts by weight based on 100% by weight of the total monomers used in the composition. If the amount is less than 0.01 part by weight, the curing rate is slow, and if it exceeds 5 parts by weight, the strength of the cured product is reduced.

If desired, further additives such as antioxidants, polymerization initiators, plasticizers, agents, thixotropic agents, silane coupling agents and dyes may be added to the compositions of the present invention in amounts that do not impair the object of the present invention.

It is a further object of the present invention to provide a laminated glass article having a cured product of the photopolymerizable resin composition described above as an inner layer and a method for producing the same. That is, according to the laminated glass product of the present invention and a method for producing the same, the glass and glass or materials other than glass and glass are prepared using the photocurable resin composition of the present invention having a volume resistivity of less than 5 × 10 ⁹ Ω · cm. By bonding, various failures due to static electricity can be predicted without the cumbersome and uneconomical way of forming a conductive coating film on the glass surface.

In the accompanying drawings, FIG. 1 is a cross sectional view of a cathode ray tube (CRT) having glass bonded to the front surface.

2 and 3 show the spraying method and the curing method of the adhesive for producing a cathode ray tube, respectively.

4 shows a method for measuring the amount of charged voltage in the examples and comparative examples of the present invention.

In these figures, numeral 1 represents the body of the cathode ray tube, (2) represents the windshield, and (3) represents the adhesive layer. With respect to Figs. 2 and 3, numeral 4 denotes an adhesive tape for sealing, 5 denotes an injection inlet of the adhesive, and 6 denotes an ultraviolet lamp. Regarding FIG. 4, numerals 7 and 8 are the sensor and recorder of the electrostatic measuring device, respectively, and 9 represents the ground line.

1 is a cross-sectional view of a cathode ray tube with glass bonded to the front surface, as a typical example of a laminated glass article. 2 and 3 illustrate a method of manufacturing the same. In the present invention, the adhesive layer is made of the above-mentioned photocurable resin having antistatic properties. Ordinary methods may be used in other respects.

Examples of other laminated glass articles of the present invention include laminated glass for doors or windows and safety glass for automobiles or other vehicles.

Next, the present invention will be described in more detail based on the following examples. However, the present invention should not be construed as limited to these specific examples. In this specification, parts and percentages refer to parts by weight and weight percent unless otherwise specified.

The following test methods were used in the examples and the comparative examples.

1. Volume resistivity

The composition was irradiated with ultraviolet light of 365 nm at 4 mW / cm 2 for 30 minutes to obtain a cured product having a diameter of 80 mm and a thickness of 2 mm. The volume resistivity of the cured product was measured according to JIS K6911.

2. Hardness

The hardness of the cured product prepared as mentioned above was measured with a Shore A durometer.

3. Spectral transmittance

The photocurable resin composition was sprayed between a pair of white glass sheets having a thickness of 3 mm to form a resin layer having a thickness of 3 mm, and then irradiated with 365 nm ultraviolet rays at 4 mW / cm 2 for 30 minutes, and a pair of white glass bonded to each other. A test fragment of the sheet was obtained. The spectral transmittance of the test fragment was measured by spectrophotometer. The wavelength of the light used for the measurement was 500 nm.

4. Measurement of charged voltage

As shown in FIG. 1, a 14 inch cathode ray tube with glass bonded to the front surface was prepared using the adhesives of Examples and Comparative Examples. A voltage of 25 kV was applied to the cathode ray tube body, and the amount of charged voltage on the windshield surface was measured with an electrostatic measuring device (FIG. 4).

The measurement of the charged voltage amount was performed twice, that is, at the time of the voltage connection and 10 seconds after the voltage cutoff.

Example 1 and Comparative Example 1

After the composition as shown in Table 1 was stirred and mixed at about 60 ° C. for 1 hour to obtain a photocurable resin composition, various tests were performed on it. The results are shown in Table 2 below.

TABLE 1

Blemmer 70 PET-800 from Nippon Oil Fats Co., Ltd .: Polyethylene glycol polypropylene glycol monomethacrylate (average molecular weight: about 800)

Blemmer 55 PET-800 from Nippon Oil Fats Co., Ltd .: polyethylene glycol polytetramethylene glycol monomethacrylate (average molecular weight: about 800)

Blemmer 50 PMEP-800B from Nippon Oil Fats Co., Ltd .: methoxypolyethylene glycol polypropylene glycol monomethacrylate (average molecular weight: about 800)

Blemmer PP-800 from Nippon Oil Fats Co., Ltd .: polypropyl glycol monomethacrylate (average molecular weight: about 800)

2-HEMA: 2-hydroxyethyl methacrylate

BEE: benzoin ethyl ether

BDK: Benzyl Dimethyl Ketal

Physical property test result

TABLE 2

Example 2

Glycol diallyl ether (average molecular weight: about 2,300, copolymerized mole ratio of ethylene oxide to propylene oxide) of the trade name Unisafe 50 DUS-230 (manufactured by Nippon Oil Fats Co., Ltd.) made of a copolymer of ethylene oxide and propylene oxide: 1 1) 230 parts of tris- (2-hydroxyethyl) isocyanurate-tris-β-mercaptopropionate (THEIC-TMP) were mixed to dissolve 0.2% benzoin ethyl ether in a solution obtained. The photocurable resin composition of the present invention was obtained and then tested. The results are shown in Table 3 below.

Example 3

Instead of 230 parts of Unisafe 50 DUS-230, glycol diallyl ether (average molecular weight: about 1,800, ethylene oxide) of the trade name Unisafe PKA-6203 (manufactured by Nippon Oil Fats Co., Ltd) manufactured from a copolymer of ethylene oxide and tetrahydrofuran A photocurable resin composition of the present invention was prepared in the same manner as in Example 2, except that 180 parts by weight of the copolymer molar ratio of tetrahydrofuran was used, and then tested. The results are shown in Table 3 below.

Example 4

Instead of 230 parts of Unisafe 50 DUS-230, 55 parts of polyethylene glycol dimethacrylate (average molecular weight: about 550) under the name NK Ester 9G (manufactured by Shinnakamura Kagaku Kogyo KK) were used in the same manner as in Example 2, except that After preparing the photocurable resin composition of the present invention, it was tested. The results are shown in Table 3 below.

Comparative Example 2

Instead of 230 parts of Unisafe 50 DUS-230, the same as in Example 2, except that 300 parts of polypropylene glycol allyl ether (average molecular weight: about 3,000) under the trade name Unisafe PKA-5018 (manufactured by Nippon Oil Fats Co., Ltd.) were used. After preparing the photocurable resin composition in a manner, it was tested. The results are shown in Table 3 below.

Comparative Example 3

In the same manner as in Example 2, except that 68 parts of polypropylene glycol dimethacrylate (average molecular weight: about 680) under the trade name NK Ester 9PG (manufactured by Shinnakamura Kagaku Kogyo KK) was used instead of 230 parts of Unisafe 50 DUS-230. After preparing a photocurable resin composition, it was tested. The results are shown in Table 3 below.

Physical property test result of hardened product

TABLE 3

Examples 5 and 6 and Comparative Examples 4 and 5

As shown in Table 4 below, an N / thiol type photocurable resin composition having an equivalent ratio of C = C to -SH of about 1 to 1 was prepared, and then the physical properties of the related cured products were tested. The results are shown in Table 4 below.

Physical test results of the composition and the cured product

TABLE 4

^* NK Ester 1G: Ethylene Glycol Dimethacrylate (manufactured by Shinnakamura Kagaku Kogyo KK)

^{* *} :% Mean content in the total composition.

Example 7

100 parts of glycol monomethacrylate (average molecular weight: about 800) of the brand name Blemmer 70 PEP-800 (manufactured by Nippon Oil Fats Co., Ltd.) and 0.2 parts of benzoin ethyl ether prepared from a copolymer of ethylene oxide and propylene oxide. Stirring and mixing at 1 ° C. for 1 hour yielded an acrylate type photocurable resin composition (Composition A).

Using composition A, the physical properties and the charge voltage amount of the cured product were measured. In order to prepare a test piece and a cathode ray tube of the cured product, ultraviolet irradiation was carried out at 4 mW / cm 2 for 30 minutes. The results are shown in Tables 5 and 6 below.

Example 8

115 parts of glycol diallyl ether (average molecular weight: about 2,300) of the trade name Unisafe 50 DUS-230 (manufactured by Nippon Oil Fats Co., Ltd) made of a copolymer of ethylene oxide and propylene oxide, tris- (2-hydroxyethyl 18 parts of) -isocyanurate-tris- beta -mercapto propionate and 2.7 parts of benzoin ethyl ether were stirred and mixed at 60 ° C for 1 hour, thereby preparing a polyene / polythiol type photocurable resin composition (composition B) Obtained.

The test was conducted in the same manner as in Example 7, except that Composition B was used instead of Composition A. The results are shown in Tables 5 and 6 below.

Comparative Example 6

A test was carried out in the same manner as in Example 7, except that instead of Composition A, an acrylate type photocurable resin of the trade name Hardrock CRT-1 (manufactured by Denki kagaku Kogyo K.K.) was used. The results are shown in Tables 5 and 6 below.

Comparative Example 7

Instead of Composition A, heat-cured at 80 ° C. for 90 minutes using an unsaturated polyester resin in the form of two packs (trade name Rigorack F-73MB, manufactured by Showakobunshi Kogyo KK, main ingredient / hardener: 100/2) Except that, the test was conducted in the same manner as in Example 7. The results are shown in Tables 5 and 6 below.

Physical property test results of cured adhesive

TABLE 5

Charge voltage of CRT windshield (unit: kV)

TABLE 6

As described above, the photocurable composition of the present invention is antistatic of a volume resistivity of less than 5 × 10 ⁹ Ω · cm, which has not been achieved by the prior art, without compromising the desirable properties of the conventional photocurable resin for glass lamination. To provide a cured product having properties. In addition, the laminated glass articles of the present invention having a cured product as the inner layer prevent various failures due to static electricity and are very useful for laminating non-reflective glass, for example, on cathode ray tube screens.

Claims (4)

A laminate comprising a photocurable resin composition composed mainly of a radically polymerizable monomer having two or more ethylene oxide repeat units in a molecule and a photopolymerization reaction initiator as an inner layer, the volume resistivity of the cured product thereof being less than 5 × 10 ⁹ Ω · cm glassware. The laminated glass article of claim 1, wherein the laminated glass article is a cathode ray tube having a glass bonded to a front surface thereof. Bonding a plurality of glass sheets using a photocurable resin composition consisting primarily of a radically polymerizable monomer having two or more ethylene oxide repeat units in a molecule and a photopolymerization reaction initiator, wherein the cured product of the composition is 5 × 10 ⁹ A method for producing a laminated glass article having a volume resistivity of less than Ω · cm. 4. The method of claim 3, wherein the laminated glass article is a cathode ray tube having glass bonded to the front side.