JPH0912344A - Laminated glass - Google Patents

Abstract

PURPOSE: To enable sticking with simple equipment and to obtain a laminated glass using an ethylene.α-olefin copolymer and excellent in impact resistance and transparency without deteriorating easy handleability or adhesiveness. CONSTITUTION: A copolymer consisting of ethylene and 3-20C unsatd. chain hydrocarbon having one double bond at the α-position and having 0.1-50g/10min melt flow rate and 0.850-0.935g/cm<3> density, a silane coupling agent and an org. peroxide are brought into a reaction by heating and the resultant modified body is held between plural glass sheets to obtain the objective laminated glass.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a copolymer of ethylene and an unsaturated chain hydrocarbon having 3 to 20 carbon atoms and having one double bond at the α-position (hereinafter referred to as α-olefin). The present invention relates to a laminated glass in which a modified product obtained by heating and reacting a silane coupling agent and an organic peroxide is sandwiched between a plurality of glasses.

[0002]

2. Description of the Related Art Conventionally, polyvinyl butyral resin has been generally used as an interlayer film for laminated glass.
However, polyvinyl butyral-based resin requires expensive equipment such as an autoclave for bonding.
In addition, it has a problem that when it is formed into a sheet, it is easy to block and the handling is complicated.

Instead of the polyvinyl butyral resin, for example, in Japanese Patent Laid-Open No. 196747/1982, a thermosetting resin containing an ethylene / vinyl acetate copolymer and an organic peroxide is interposed between glass plates to be integrated. A laminated glass in which a thermosetting resin layer is thermoset has been proposed. Further, in JP-A-4-198046, acid-modified saponified ethylene.
A resin composition for a laminated glass interlayer film mainly composed of a vinyl acetate copolymer has been proposed.

[0004]

The object of the present invention is to bond ethylene with a simple equipment, easy handling, without impairing adhesiveness, excellent in impact resistance and transparency.
An object is to provide a laminated glass using an α-olefin copolymer.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an ethylene / α-olefin copolymer. It came to completion.

Hereinafter, the present invention will be described in detail.

In the present invention, the one used between a plurality of glasses has a melt flow rate (MFR) of 0.1 to 0.1.
50g / 10 minutes, density 0.850-0.935g / c
It is a modified product obtained by reacting a copolymer of ethylene and α-olefin consisting of m ³ with a silane coupling agent and an organic peroxide component by heating.

The copolymer of ethylene and α-olefin has (1) the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by the gel permeation chromatography (GPC) method. / Mn) is 3 or less (2) The ratio of the average number of branches in the high molecular weight region 30% and the average number of branches in the low molecular weight region 30%, which are fractionated by the gel permeation chromatography (GPC) method, is
It is preferably 0.8 to 1.2. Moreover, you may use these individually or as a mixture of 2 or more types.

Examples of ethylene / α-olefin copolymers include copolymers of ethylene and α-olefins, multi-component copolymers of ethylene and two or more types of α-olefins, and the like. These α-olefins have 3 carbon atoms in order to obtain a copolymer having excellent low temperature adhesiveness and adhesive strength.
It is preferred to use .about.20 .alpha.-olefins. Specific examples include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like.

The MFR (melt flow rate) of the ethylene / α-olefin copolymer used in the present invention is JIS
According to K 6760, it was measured at 190 ° C. under a load of 2160 g. M of ethylene / α-olefin copolymer
If the FR is less than 0.1 g / 10 minutes or more than 50 g / 10 minutes, there is a problem in molding when forming the interlayer film for laminated glass, which is not preferable in practice and is not suitable for laminated glass.

The density of the ethylene / α-olefin copolymer is based on JIS K 6760, and after immersing the test piece in hot water at 100 ° C. for 1 hour, the test piece left to cool to room temperature has a density gradient kept at 23 ° C. Measured with a tube. Density is 0.935g / c
If it exceeds m ³ , adhesiveness to glass and transparency are poor,
If it is less than 0.850 g / cm ³ , the tackiness is large and the handling is difficult. In any case, it is not preferable in practical use.
Not suitable for laminated glass.

In the present invention, Mw / Mn is the weight average molecular weight (Mw) and number average molecular weight (Mn) determined by GPC (gel permeation chromatography).
It is the ratio of M and M to maintain the adhesive strength and transparency.
w / Mn is preferably 3 or less.

This measurement is carried out using a high temperature GP manufactured by Waters Co.
C device "ALC / GPC150C", Tosoh Corporation "TSKgel GMHHR-H (S)" column 7.
Equipped with 8 mm inner diameter x 30 cm x 3 pieces, using 1,2,4-trichlorobenzene (TCB) solvent, temperature 140
℃, flow rate 1.0ml / min, injection concentration 30mg / 30m
1 and the injection amount was 300 μl. The elution volume was calibrated by the universal calibration method using standard polystyrene manufactured by Tosoh Corporation.

The average number of branches of the ethylene / α-olefin copolymer in the high molecular weight region of 30% (number / 1000C) and the average number of branches of 30% in the low molecular weight region (number / 1000C) of the ethylene / α-olefin copolymer fractionated by GPC The ratio of and is preferably 0.8 to 1.2 in order to maintain adhesive strength and transparency. Of the total amount eluted by GPC, the first eluted 30% is the high molecular weight region, the subsequently eluted eluent is the peak molecular weight region, and the last eluted 3
0% was defined as the low molecular weight region.

The average number of branches of each molecular weight region component fractionated by GPC is 100 carbon atoms by connecting "FT-IR 1760X" manufactured by Perkin Elmer Co., Ltd. to the above GPC device.
It was determined as the number of carbon branches per 0.

The method for producing the ethylene / α-olefin copolymer used in the present invention is illustrated below.

The production of the copolymer is described in JP-A-58-19.
309, JP-A-60-35006, and JP-A-60-3
No. 5007, catalysts of metallocene and alumoxane disclosed in JP-A-3-188092, Japanese Patent Publication No. 1-50195.
No. 0 and WO92 / 01723, and the like, a catalyst comprising a metallocene and a compound which reacts with the metallocene to form a stable ion, or JP-A-3-1.
Specific metallocenes described in International Patent Publication No. 63088 and International Patent Publication No. WO93 / 08221, that is, constrained geometry type catalysts can be used.

The copolymer is an organic transition metal compound containing a metallocene, that is, a cyclopentadienyl derivative, a compound which reacts with the compound to form an ionic complex,
And / or in the presence of a catalyst consisting of an organometallic compound,
It can be produced by copolymerizing ethylene and α-olefin, but is not limited thereto.

Examples of the copolymerization method of ethylene and α-olefin include a gas phase method, a slurry method, a solution method and a high pressure method. However, in the solution method, the polymerization is carried out in the presence of a large amount of solvent. However, a large amount of the solvent remains in the polymer, which is not preferable. On the other hand, in the high-pressure method, since the polymerization is carried out in a state where the monomer concentration is very high, the polymerization activity can be significantly increased, and the residual amount of the solvent and the low molecular weight component can be significantly reduced. Also in the gas phase method, since the polymerization is carried out in the absence of a solvent, the solvent does not remain in the polymer.

The high pressure method referred to here is the special table 1-5.
03788, European Patent Application Publication No. 612769.
It is what is described in the issue. In a stirred reactor,
And divide the inside of the reactor into at least three chambers, and
Polymerization is performed in a reactor under high pressure of 0 to 2,500 kg / cm ² , and the polymerization temperature depends on the productivity of the copolymer.
The range of 0-300 degreeC is preferable.

The polymerization in the gas phase method is preferably carried out by using a catalyst component preliminarily polymerized with an olefin, an organoaluminum compound and an ionized ionic compound in order to enhance the polymerization activity.

The ethylene / α-olefin copolymer obtained from the polymerization method using the metallocene type catalyst as shown in the exemplified publication shows that the low molecular weight component which causes stickiness increases rapidly even if the density is lowered. However, a copolymer having a low density region can be realized, and when the polymerization is carried out by a high pressure polymerization method, a gas phase polymerization method or the like, a residual solvent is small, and thus excellent low temperature adhesiveness and transparency can be easily realized.

The organic peroxide used in the present invention may be, for example, ketone peroxide such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3, or the like.
3,5-trimethylcyclohexanone peroxide,
Methyl cyclohexanone peroxide, acetylacetone peroxide, methyl acetoacetate peroxide, etc. are used as peroxyketals, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t -Butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-hexylperoxy) ) 3,3,5-Trimethylcyclohexane, 1,1
-Bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclododecane and the like, as hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1 , 1,
3,3-tetramethylbutyl hydroperoxide,
t-hexyl hydroperoxide, di-isopropylbenzene-bis-hydroperoxide and the like are dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α ′. -Bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5
-Bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3 and the like, acetyl peroxide, isobutyryl peroxide, octa as diacyl peroxide. Noyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, stearoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, etc. Examples of oxydicarbonates include di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate and bis- (4-t-butylcyclohexyl) peroxydicarbonate. Carbonate, di-myristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxydicarbonate, di- -Allyl peroxydicarbonate and the like, as peroxy ester, (a-bis-neodecanoylperoxy) di-isopropylbenzene, cumylperoxy neodecanoate, 1,1,3,3-tetramethyl Butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-di- Methyl-2,5-bis (2-ethylhexanoylperoxy) hexane, , 1, 3,
3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,
1,3,3-Tetramethylbutylperoxyisopropyl monocarbonate, t-butylperoxylaurate, t-butylperoxy-3,3,5-trimethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t -Butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxymaleic acid, t-hexylperoxybenzoate, t-butyl Peroxybenzoate, bis-t-butyl peroxyisophthalate, etc. can be used. The proportion of the organic peroxide is preferably 5 parts by weight or less with respect to 100 parts by weight of the ethylene / α-olefin copolymer used in the interlayer film.

Further, triallyl isocyanurate or the like may be used as a curing aid. The mixing ratio is preferably 10 parts by weight or less with respect to 100 parts by weight of the ethylene / α-olefin copolymer used in the interlayer film.

In the present invention, a silane coupling agent is used as the adhesion improver. As a silane coupling agent,
Vinyltrichlorosilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ -Glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl)
γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be mentioned. The blending amount of these silane coupling agents is 5 parts by weight or less with respect to 100 parts by weight of the ethylene / α-olefin copolymer used in the interlayer film.

In addition, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, rosins, low molecular weight styrene resins, etc. for improving the adhesion to glass. It is also possible to blend the tackifier and the like. Further, as long as the effects of the present invention are not impaired, antioxidants, surfactants, antiblocking agents, lubricants, flame retardants, light stabilizers, ultraviolet absorbers, organic / inorganic fillers, colorants, plasticizers, if necessary. Additives generally added to thermoplastic resins, such as agents, nucleating agents, clarifying agents, and catalyst neutralizing agents, may be added.

The modified product obtained by the present invention may be used by forming it in an intermediate film, and the method for producing the intermediate film is not particularly limited, but the processing method is, for example,
Extrusion molding, calender molding, blow molding, injection molding, casting and the like can be mentioned. The thickness of the interlayer film of the laminated glass is not particularly limited, but 0.1 to 2 mm is preferable. If the thickness is less than 0.1 mm, the penetration resistance of the laminated glass decreases, and if it exceeds 2 mm, the cost increases, which is not preferable.

In order to give the laminated glass a decorative property and increase the added value, the interlayer film may be made into two layers, and a resin for decoration, cloth, wood cutting, etc. may be sandwiched between the two layers. .

To produce a laminated glass, the intermediate film may be laminated between a plurality of glasses and adhered under heating and reduced pressure.

[0030]

EXAMPLES Examples will be described below, but these are illustrative and not restrictive.

A haze was measured as a measure of the transparency of the laminated glass, a tear strength of the intermediate film was measured as a measure of impact resistance, and a boiling test was performed as a measure of adhesion, heat resistance and water resistance. The haze, tear strength, and boiling test evaluations were performed as follows.

<Haze> Measured in accordance with ASTM D 1003. The laminated glass is preferably 1.0% or less.

<Tear Strength> In accordance with JIS K 6301, the tear strength was measured without notching. The tear strength is measured by the resin sheet for interlayer film alone, and the impact resistance of the laminated glass correlates with the tear strength of the interlayer film. Higher values are preferred.

<Boiling test> Measured in accordance with JIS K3205. The value obtained by subtracting the haze before boiling from the haze after boiling was displayed. The smaller the value, the better.

Embodiment 1

[0036]

[Table 1]

As shown in Table 1, an ethylene / 1-butene copolymer (density: 0.908 g / cm ³ , MFR: 2.3)
g / 10 minutes, Mw / Mn: 2.3, high molecular weight region 30%
Average number of branches / 30% of low molecular weight region: 1.
1) 100 parts by weight of 1,1-as organic peroxide
2 parts by weight of bis (t-butylperoxy) 3,3,5-trimethylcyclohexane “Perhexa 3M” (manufactured by NOF CORPORATION), γ-methacryloxypropyltrimethoxysilane “KBM503” as a silane coupling agent.
0.5 part by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) was blended. These are melt-mixed with an extruder at 150 ° C. and the thickness is 0.4 m.
m was extruded. This intermediate film (sheet)
Was cut so that the peripheral portion was larger than the shape of the glass plate by 1 to 2 cm, and sandwiched between two clean glass plates without wrinkles. Next, the laminated body thus obtained was inserted into a bag, and the inside of the bag was depressurized by using a vacuum pump so that the inside of the bag was 30 Torr or less. After 10 minutes, the bag was taken out of the heating furnace, returned to atmospheric pressure, and then allowed to cool. The cooled laminated glass was washed, the excess film protruding to the periphery was cut off, and the periphery was chamfered to obtain a product.

The results are shown in Table 1. Excellent in haze, tear strength and boiling test.

Example 2 As shown in Table 1, the organic peroxide "Perhexa 3M" was mixed with 3
A sample was obtained in the same manner as in Example 1 except that the weight part was changed.

The results are shown in Table 1. Excellent in haze, tear strength and boiling test.

Example 3 As shown in Table 1, an ethylene / 1-butene copolymer (density: 0.895 g / cm ³ , MFR: 3.4 g / 10
Min, Mw / Mn: 2.0, average branch number of high molecular weight region 30% / average branch number of low molecular weight region 30%: 1.1) except that the sample was obtained in the same manner as in Example 1. It was

The results are shown in Table 1. Excellent in haze, tear strength and boiling test.

Comparative Example 1 As shown in Table 1, a sample was obtained in the same manner as in Example 1 except that the organic peroxide "Perhexa 3M" and the silane coupling agent "KBM503" were not added.

The results are shown in Table 1. Satisfaction with the haze and boiling tests was not obtained.

Comparative Example 2 As shown in Table 1, a sample was obtained in the same manner as in Example 3 except that the organic peroxide "Perhexa 3M" and the silane coupling agent "KBM503" were not added.

Table 1 shows the results. Satisfaction with the haze and boiling tests was not obtained.

Comparative Example 3 As shown in Table 1, ethylene-vinyl acetate copolymer "Ultrasen 627" (manufactured by Tosoh Corporation, vinyl acetate content: 20% by weight, density: 0.940 g / cm ³ , MF)
R: 0.8 g / 10 min), except that the sample was obtained in the same manner as in Example 2.

The results are shown in Table 1. Satisfactory results were not obtained in haze, tear strength and boiling test.

[0049]

Industrial Applicability As described above, according to the present invention, ethylene / α, which can be pasted with simple equipment, is easy to handle and does not impair adhesiveness, and has excellent impact resistance and transparency.
-It is possible to provide a laminated glass using an olefin copolymer.

The laminated glass is used for windshields and side windows of automobiles, window glass of buildings, etc.
Further, since the loss factor of the interlayer film (resin layer) of the laminated glass can be increased, it is also suitably used for soundproof glass and the like.

Claims (2)

[Claims] 1. A melt flow rate (MFR) of 0.1.
50g / 10 minutes, density 0.850-0.935g / cm
Of ^3, a copolymer of an unsaturated chain hydrocarbon having 3 to 20 carbon atoms in the ethylene and α-position having one double bond, and the silane coupling agent and an organic peroxide heated reaction obtained A laminated glass obtained by sandwiching a modified product between a plurality of glasses. 2. A copolymer of ethylene and an unsaturated chain hydrocarbon having 3 to 20 carbon atoms having one double bond at the α-position, wherein (a) the melt flow rate (MFR) is 0.1 to 0.1. 50 g
/ 10 min (b) Density is 0.850 to 0.935 g / cm ³ (c) Ratio (Mw) of weight average molecular weight (Mw) and number average molecular weight (Mn) determined by gel permeation chromatography. / Mn) is 3 or less. (D) The ratio of the average number of branches in the high molecular weight region 30% and the average number of branches in the low molecular weight region 30%, fractionated by the gel permeation chromatography method, is 0.8 to 1.
2. The laminated glass according to claim 1, wherein the laminated glass is 2.