JPH02183079A - Improved window material - Google Patents

Abstract

PURPOSE:To adapt the title window material to usage under wide environmental conditions regardless of temperature by injection-molding a thermoplastic resin composed of a crystalline ethylene-propylene block copolymer, etc. onto the outer circumference of pane glass and unifying the resin with the plane glass. CONSTITUTION:A thermoplastic resin consisting of each specific quantity of a 30-70pts.wt. crystalline ethylene-propylene block copolymer A, a 5-50pts.wt. modified block copolymer B, a 0-40pts.wt. hydrogenated block copolymer and 10-30pts.wt. crystalline polyethylene is constituted. The thermoplastic resin is injection-molded onto the outer circumference of a pane glass and unified. A+B+C+D=100pts.wt. holds, and the ratio of A to D is brought to the specific ratio of 80/20-50/50. Specific quatities of the ethylene content of A of 5-20wt.% and the content of the vinyl aromatic compounds of B and C of 5-95wt.% are used, and polyethylene, density of which of 0.945g/cm<3> or more is specified, is employed as D.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention provides temporary glass and frames that do not lose their characteristics even under a wide range of environments from high temperatures to low temperatures. It is integrally molded by resin or ink-1 molding and closes on the window material that is in good contact with the window material.

[Conventional technology]

Conventionally, window materials for vehicles such as automatic train cars, architectural windows, electrical appliances, and window materials for home use were made using Karasu QP's transparent VJ and the window frame separately. (It was common to be assembled mainly by hand. However,
Since this method has poor cattle resistance, there has long been a desire for an efficient production method.

In order to meet this demand, we placed the transparent (A diagonal) of the crow screen in the index mold, and placed window frame material around it.
How to make a window (manufacturing Δ) in which the glass and frame are integrated by molding ('t,'r public 11rf 61-7368
(see Publication No.) is proposed. In addition, methods have also been proposed in which the window material and the window frame (A) are backed up (see Japanese Patent Application Laid-open No. 15716/1983). However, there were also problems with rubber, and there was a demand for the development of a better material for window frames.

On the other hand, JP-A-63-25005. Publication F3 discloses a technique for obtaining a composition in which a polyolefin resin containing carboxyl groups, etc. is blended with a thermoplastic elastomer of styrene or olefin as a window frame material that is integrally molded with plate glass. ing. However, unlike vulcanized rubber, this thermoplastic laminated resin has a high resistance to IjA.
There was a problem that the ID property was poor and therefore it could not be practically used for light rain.

Window frame materials used in window materials manufactured by integrally molding temporary glass are required to have appropriate surface hardness, flexibility (rigidity), impact resistance, etc. In this regard, the present inventors conducted research and found that among the existing materials, a composition of polyb[1-pyrene and hydrogenated vinyl aromatic compound-conjugated diene block comonomer] satisfies the above requirements. met and turned out to be the best.

However, even in this composition, platy crow is used in one.
If the window material is integrally molded with No. 1 portion,
If the sword lath is on a curved surface, there is a problem that the lath may break, and the welt part of the window frame may break or fall off the glass. It needed improvement.

Therefore, the present inventors have discovered the excellent characteristics of a composition consisting of polypropylene and a hydrogenated vinyl aromatic compound-conjugated diene block copolymer, including good surface hardness, rigidity, and impact resistance. Hato/ν drops to 12 degrees,
! Low temperature at 121! ! ? We earnestly considered improving 1↑(1 (low?Low rigidity at A+'+).

Generally, as a resin that improves the low 2Sa impact properties of poly 1[1 pyrene, there is a crystalline ethylenep 1"pyrene 1=+tsuk copolymer, which is combined with the aforementioned hydrogenated vinyl aromatic compound-conjugated diene resin. [Even if it is combined with one copolymer, the window frame +4 slope that is the object of the present invention cannot be obtained (
There was no 57. Therefore, the present inventors discovered a technique to combine this with crystalline polyethylene, and found that this composition has significantly lower temperature properties than when using a single polymer with the same ethylene/propylene ratio. After discovering that these three components were excellent, a patent application was filed for a window frame made by molding a composition using these three components into a sheet glass.

(Problems to be Solved by the Invention) However, window materials using the three components described above have poor adhesion to sheet glass, so if a large force is applied to the window frame, the window frame will come off. The solution to this problem was to apply adhesive to the temporary crow,
It is also possible to injection mold the composition after that, but 1
As the number of steps increases, the number of contact points between the plate glass and the composition after molding (14) is that applying adhesive is technically difficult and troublesome, and the contact points are However, there was a problem in that the 71iL paint was not very effective.

Therefore, the present inventors investigated the surface hardness, rigidity, and
Inspection 1 was carried out to improve the right contact with the plate crow of the in-4 note molding 11) without any deterioration in impact resistance, low temperature properties, etc.

[Means to solve the problem]

By the way, as a means to improve the adhesion of polyolefins and hydrogenated polymers to various adherends, avoid bonding molecular units containing carboxylic acid groups or derivative groups thereof. For example, Japanese Patent Application Laid-Open No. 63-2500 discloses a technique of coating using a blend of polyA lenoin resin containing C471 containing Calxyl Fushu.

The present inventors have discovered that when carboxylic acid groups, etc. are bonded to a composition consisting of a crystal 11]-brecy 1-1 birenbu 11 co-synthesis, a hydrogenated monopolymer, and crystalline polyethylene, As a result of detailed examination of the effect, it was surprisingly found that hydrogenated block J (polymer) was used as a small polymer for bonding carboxylic acid groups; , it has much better adhesion with temporary crow, and even if part or all of the hydrogenated block copolymer is replaced with a hydrogenated block copolymer bonded with carboxylic acid groups, etc., the original composition remains the same. The present invention was achieved by discovering that the good properties of the product are hardly impaired.

However, the present invention provides a window material in which a sheet glass is integrated into an injection mold, and a resin is integrated with a sheet glass obtained by injecting a thermoplastic resin into all or a part of the outer periphery of the sheet glass. The thermoplastic resin comprises (a) 30 to 70 parts of a crystal/[(1-ethylene propylene block copolymer); (b) at least one polymer block A mainly composed of a vinyl aromatic compound; A modified block copolymer 5 in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to a hydrogenated block copolymer containing at least one polymer block B mainly composed of a hydrogenated conjugated diene compound. ~50 parts by weight, (c) at least one monopolymer block A mainly composed of a vinyl aromatic compound, and at least t polymer block B mainly composed of a hydrogenated conjugated diene compound. ) Is there one? (d) 10 to 40 parts by weight of a hydrogenated block copolymer; and (d) 10 to 40 parts by weight of a hydrogenated block copolymer;
This is an improved window material that has one feature: a resin composition consisting of 30 parts of In.

The window io of the present invention has excellent productivity, and when used,
The window frame material does not soften at high temperatures, and has excellent scratch resistance (14C).
J-3 is not only highly resistant to CHI at low temperatures, but also linearly shrinks during the transition to low temperatures.

Due to the small response J, the part may be cut to 1.
It does not fall off the glass or the glass can be cut, and since the window frame and glass are glued together, the window material has the excellent feature of being hard to fall off due to the stress applied to it.

Next, each +A advantage used in the present invention will be explained.

The temporary glass used in the window material of the present invention is not particularly limited and may be any glass commonly used for windows.

There is no limitation on the shape, and for example, curved glass used in automobiles and flat glass used in other applications can be used.

The crystalline ethylene propylene block copolymer used as component (a) of the present invention has a small temperature dependence of stiffness and maintains appropriate stiffness and strong impact temperature characteristics. 20% by weight, and the boiling n-hebutane extraction residue is 70% by weight or more. In addition, in order to maintain moldability for molding the product as a resin composition, the melt flow index (L) is set to 1.
~100 or less, preferably 8 to 50 or less is used.

The modified block copolymer used as component (b) of the present invention includes at least one polymer block A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a hydrogenated conjugated diene compound. It is obtained by adding an unsaturated carboxylic acid or a derivative thereof to a hydrogenated block copolymer having at least one of the following. Examples of unsaturated carboxylic acids or derivatives thereof that can be added to the hydrogenated block copolymer include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, monotonic acid, cis- 4-Cyclohexane 1,2-dicarboxylic acid J3 and its anhydride, endocis-bicyclo(2
,2,1) -5-hebutene-2,3 dicarbone WJ3
and its anhydride, 'maleimide, etc.
Among these, maleic anhydride is particularly preferred.

The above-mentioned modified block copolymer, which is a component of the composition used in the present invention, is prepared by adding an unsaturated carbon compound (4θ) to the substrate and the hydrogenated block copolymer in a solution state or a molten state. With or without the use of a radical initiator, by adding (J) to (Q), these modified blocks (J) can be produced by adding (J). However, it is not preferable to use a production method in which the modified block copolymer contains undesirable components such as gel, or in which the melt viscosity of the copolymer is significantly increased, resulting in poor processability.
For example, there is a method in which an unmodified hydrogenated block copolymer is reacted with an unsaturated carboxylic acid or its derivative in the presence of a radical initiator in an extruder.

Addition of unsaturated carboxylic acids (JL derivatives thereof to hydrogenated block copolymers;)
0.05-20 small parts per 0,000 parts, preferably 0
．． 1 to 10 parts by weight is most preferred. If the amount added is less than 0.05 parts by weight, when it is made into a composition, there will be an improvement compared to the unaltered hydrogenated block combination;
Even if the amount added exceeds 20 parts by weight, the effect of improving Lc will not increase compared to the above. The unsaturated carboxylic acids or derivatives thereof used in the present invention may be used not only alone, but also as a mixture of two or more.

Moe's hydrogenated f-lock copolymer, which is modified as a modified block copolymer, has, for example, the following structure (1 and b
or a mixture thereof.

△(B-△) ,! 3(A-B), (△-[3)
. , n (△-B) X, ([3-A-B), here for n
I'm going to pour out the rest of the liquid.

The hydrogenated black copolymer contains 5 to 95% by weight of vinyl aromatic compound, preferably 1! ] ~ 60 This includes the old P. Furthermore, mainly vinyl aromatic compounds and J
The polymer block A is a vinyl monoaromatic compound small polymer block or a vinyl aromatic compound! ) 0 weight D% or more,
Preferably, it is a copolymer block of a vinyl aromatic compound and a hydrogenated conjugated diene compound containing 70% or more, and further contains a hydrogenated copolymer.
Polymer block B mainly composed of a Q diene compound contains a hydrogenated conjugated diene compound polymer block or a hydrogenated co-1Ω diene compound at 50% by weight or more, preferably 70% by weight. A copolymer of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing the above
It is 1 tsuku. In addition, when the polymer block A mainly composed of a vinyl aromatic compound and the hydrogenated copolymer block B mainly composed of a hydrogenated diene compound are copolymer blocks, each copolymer block Hydrogenated conjugated diene compound or vinyl in the molecular chain that occurs!
The distribution of the aromatic compound may be random, devar (in which the 7-mer component increases or decreases along the molecular chain), partially block-shaped, or any combination of these, vinyl If there are 2 or more of each of a polymer block mainly composed of an aromatic compound and a small polymer block mainly composed of a hydrogenated co-1Ω diethylene compound, 71 each.
``Tsuku may each have the same structure, or may have a different structure C
It's okay to have one.

As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more It 2 fffi may be selected from among styrene, α-methylstyrene, vinyl-1-helene, p-tert-butylsubrene, etc. Among them, Styrene is particularly preferred. Additionally, hydrogenated +(
As the conjugated diene compound before hydrogenation to obtain a 1Ω diene compound, one or more compounds are selected from among, for example, butadiene, isoprene, 1,3 pentadiene, 2,3 dimedyl 1,3 butadiene, etc. , especially butadiene,
Isoprene and combinations thereof are preferred. For the combined block mainly composed of co-IQ diene compound before hydrogenation, the microstructure containing C in the block can be selected arbitrarily, for example, J3 in the polybutadiene block.
1. ? 20-50% binding, preferably 25.
45% is required.

The number average molecular weight of the hydrogenated block copolymer is 5000 to 10
00000, preferably 10000~! +00000,
It is preferably in the range of 30,000 to 200,000. Furthermore, the molecular 411i foil of the hydrogenated block copolymer may be linear, branched, radial, or any combination of these.

Present invention C/Hydrogenated 71'Jtsuk (intermediate) used
41 covers the above-mentioned structure.
'H Publication 11j;/10-237' JJ85-4 Publication) (For example, see the Currency Law).

The hydrogenated carboxylic acid compound used as component (c) of the present invention is: 51 and a hydrogenated conjugated cylindrical compound as the upper body.
(There is (b)! The hydrogenated block before the conversion to add knock copolymer 1- and + to the Jk part. The aromatic compound-containing base, each A-Fd body component, and the molecules are excluded from the same range.

However, in the present invention, the components (b) and (c) do not need to be the same in block structure, vinyl aromatic compound content, molecular legs, etc., and may be selected in any combination. can.

The crystalline polyethylene used as component (d) of the present invention is low-density polyethylene produced by a high pressure method or a medium-low pressure method,
Medium to high density polyethylene with a density of 0.945 g/C...3 or higher, preferably with a density of 0.945 g/C...3 or higher, in order to maintain a balance between low stress generated at low temperatures, moderate rigidity and high impact strength properties. From the viewpoint of moldability for molding products as a resin composition, the melt index ('l) is 1 to 50, preferably 2.5.
~30.

Component (a), the crystalline EDLEMP ``1 Pyrenbu 1'' copolymer, is contained in an amount of 30 to 70 parts by weight, preferably 35 to 60 parts by weight, per 100 parts by weight of the entire resin composition.

If the above-mentioned ○ content is less than 30 parts by weight, it is not preferable from the viewpoint of maintaining the appropriate rigidity targeted by the present invention, particularly maintaining rigidity at high temperatures above room temperature and scratch resistance. Moreover, if the amount exceeds 70 parts by weight, the stress generated at low humidity will be undesirable. Also, 1? I is below room temperature (It temperature side rule・1to1
becomes large, which is also undesirable from the standpoint of holding Shoseki Toku 1i.

The modified block copolymer as component (b) is contained in the total resin composition in an amount of 5 to 50 parts by weight, preferably 10 to 10 parts/IQ part by weight.

Component (c), the hydrogenated polyester copolymer, is contained in the total resin composition in an amount of 0 to 40 parts by weight, preferably 10 to 30 parts by weight.

The total amount of components (b) and (c) is preferably 20
-50 parts by weight, and in the above cases, if the TI amount is less than 20 parts by weight, stress generated at low temperatures will increase, and it will be difficult to maintain appropriate flexibility and maintain street durability at low temperatures below room temperature. It becomes slightly inferior in terms of points. Further, if the thickness exceeds 50,712 fi parts, it becomes somewhat inferior in terms of maintaining appropriate rigidity, especially maintaining rigidity at high temperatures above room temperature, and in terms of scratch resistance.

If the content of component (b) is less than 5,000♀ parts (1), it is unfavorable in terms of adhesion to the plate glass, and if it exceeds 50 parts by weight, hygroscopicity increases and the appearance of the molding mouth is poor. (2) This is undesirable because it tends to cause deterioration and functional changes due to moisture absorption.

Component (d) crystalline polyethylene is contained in 10% of the total resin composition.
~30 single ω parts are included. If the content is outside the above range, the cracks that occur at low temperatures may become too large, and the rigidity or resistance to 1 corrosion within j may be maintained or ta! This is undesirable as it may reduce scratch resistance.

The resin composition used in the present invention can be achieved by combining the above-mentioned components, but it is generally preferable to
(a) component crystalline ethylene propylene block copolymer and (d) component in 100 parts by weight of the resin composition of the present invention;
The total amount of component crystalline polyethylene is 50 to 80 parts by weight, preferably 55 to 75 parts by weight, and the ratio of crystalline ethylene propylene to crystalline polyethylene is 80/20.
50,150, more favorable results can be obtained from the target viewpoint of the present invention.

The resin composition consists of the above-mentioned essential components, but if necessary, antioxidants, ultraviolet and ray absorbers, light stabilizers, pigments, moldability improvers, etc. can be added.

In addition, other thermoplastic resins, especially carboxylic acid-modified polyΔrefine, inorganic fillers, etc., may not be used, unless the purpose of the present invention, such as maintaining low-temperature response, appropriate rigidity, impact properties, and scratch resistance, is achieved. Agents etc. may be added.

The window material of the present invention can be manufactured by injecting the above-mentioned temporary glass into an injection mold and injection-molding the above-mentioned thermoplastic resin composition on all or part of the outer periphery of the temporary glass. I can do it. At that time, a layering agent may be applied in advance to all or part of the glass surface that the resin composition contacts, and the resin composition may be contacted at the same time as the inlet molding.

The injection molding strip 11 may also be the same as the strip f1 for molding general polyp[]1pyrene, and is not particularly limited.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to the following Examples.

J3, various types of sacrificial materials used in the following examples are as follows.

■Plate glass: Flat glass untreated product ■Crystalline ethylenebu] Copylene block copolymer PP
2 [Dyrene content 10% M1 scream (L) 14V/10 minutes ■ Modified block copolymer M I-I S [3 Styrene-butadiene [1] Hydrogenated copolymer Maleic anhydride added to Plano 1 - Sudylene content 35% Maleic anhydride addition amount 1% MFI (L-row I't) 2 g/10) ■ Hydrogenated block copolymer 1-I S B Hydrogenated compound of styrene-butadiene block covalent combination Soubrene content 30% MFI (L strip I't) 39/10 minutes ■ Crystalline bamboo polyethylene P [density 0.965 MFI (E strip I 4) b 9 /10 minutes■ Adhesive Nijiran coupling agent Also, Table 1 shows the formulation d5 and its amount water properties of the compositions made from Des 1 to 1.

The compositions were blended using a 2IIIll extruder at 210°C, and the base water properties shown in the table were measured by the following J method.

JIS K7301 flexural modulus
JIS 7203 1~Impact value JIS K7110
1 Ky (16 mesh passes) of river sand was dropped from a height of 50 cm and applied to a piece of sand at a 45 degree angle, and the surface condition was observed.

(◎ Excellent, ○Good,
The molded product shown in FIG. 1 was injection molded with a glass plate inserted. The injection molding temperature was 220'C.

The window frame of the molded product was shiny and had a good feel.

When the window frames of these molded products were pulled in the direction of removal, none of them came off easily and the adhesion to the glass was extremely good.

Furthermore, these molded products were left in environments of -40°C and 80°C for several hours for several hours, but no abnormalities were observed.

Comparative Example 1 The same test as in Example 1 was conducted using the composition of Nα7 in Table 1. The appearance of the molded product was good IJ7, but the window frame and glass were completely adhered to J3, and when it was left at -4.0°C, breakage of the weld part was observed. This is thought to be due to the low weld strength and high rigidity at the gate, which caused a large amount of force to be applied to the weld part.

Comparative Example 2 A test similar to that in Example was conducted using the Na8 composition shown in Table 1. The appearance of the molded product is good, and the temperature at 40°C and 8
Even though J3 was in an environment of 0 degrees Celsius, there was no abnormality; the window frame and glass were still glued together, but when the window frame was pulled outwards at temperatures above room temperature, it separated.

Comparative Example 3 The same test as in Example 1 was conducted using compositions No. 9 and 10 in Table 1. In the molded product using NQIO, the window frame material was soft, and the window frame was deformed by small horns during handling. The adhesion between the window frame and the glass was good and rarely happened, but after leaving these molded products at 80'C, when they were taken out, marks were found on the window frame where the work gloves had been worn.

N (11-6 molded products r + Yuko J, nothing bad happened.

Example 2 Using the composition No. 2.4 in Table 1, FJi of the window frame:
A bonding agent was applied to the glass surface in advance, and the strip 11 was made the same as in Example 1, and the molded product shown in FIG. 3 was injection molded.

The external appearance of the jq rad molded product was good, and no abnormalities were observed in environmental tests at -40"C and 80°C.

Comparative Example 4 Using the composition of Nα11 in Table 1, the same test as in Example 1 was conducted. Although the appearance of the molded product was good, -40
When left in the 'C environment for 3 hours, cracks appeared in the weld part. This is thought to be because the composition became hard at low temperatures and at the same time was subjected to strong shrinkage stress.

〔Effect of the invention〕

The window material of the present invention is not only easy to mold, but also has a good glossy appearance, has good adhesion between the window frame and glass, and has excellent durability of the window frame even in the field temperatures. It has the excellent characteristics of having excellent scratch resistance and no breakage of parts at low temperatures, and is an excellent window material that can be used under a wide variety of environmental conditions.

[Brief explanation of the drawing]

FIG. 1 is a front view of a molded window material integrally molded with window frame material around the entire circumference, and FIG. 2 is a sectional view thereof. Figure 3 is a front view of a window material molded product in which a window frame (A) is molded on a part of the Jj whitebait. 1...Flat crow 2...Window frame material 3...Gate part 4...・Weld part 5...Glass surface back-grinding coding special Δ'1 Applicant: Asahi Kasei Industries, Ltd. Nissan Jidosha Co., Ltd.

Claims (1)

[Scope of Claims] 1. A window material in which a plate glass is integrated with a resin obtained by inserting a plate glass into an injection mold and injection molding a thermoplastic resin on all or part of the outer periphery of the plate glass. The thermoplastic resin contains (a) 30 to 70 parts by weight of a crystalline ethylene propylene block copolymer, (b) at least one polymer block A mainly composed of a vinyl aromatic compound, and a hydrogenated conjugated diene. 5 to 50 parts by weight of a modified block copolymer in which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to a hydrogenated block copolymer having at least one polymer block B mainly composed of a compound;
(c) Hydrogenated block copolymers 0 to 40 having at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a hydrogenated conjugated diene compound parts by weight, and (d) 10 to 30 parts by weight of crystalline polyethylene (a+b+c+d=1
1. A window material with improved adhesion between a frame material and glass, characterized in that it is a resin composition consisting of 0.00 parts by weight). 2. The window material according to claim 1, wherein the ratio of the crystalline ethylene propylene block copolymer as the component (a) to the crystalline polyethylene as the component (d) of the resin composition is 80/20 to 50/50. 3. The window material according to claim 1, wherein the crystalline ethylene propylene block copolymer as component (a) has an ethylene content of 5 to 20% by weight. 4. The window material according to claim 1, wherein the vinyl aromatic compound content of the modified block copolymer and hydrogenated block copolymer of component (b) and component (c) is 5 to 95% by weight. 5. The crystalline polyethylene of component (d) has a density of 0.94
The window material according to claim 1, which is a medium or high density polyethylene having a density of 5 g/cm^3 or more. 6. The window material according to claim 1, wherein all or a portion of the contact area between the injection molded resin composition and the inserted plate glass is bonded with an adhesive.