JPH04504273A - Molding materials for producing films for laminated safety glass - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Molding materials for producing films for laminated safety glass field of technology The present invention provides a plasticized, partial Partially acetalized polyvinyl alcohol, especially partially butyralized Synthesis based on polyvinyl alcohol (polyvinyl butyral, PVB) Molding materials and composites for producing laminated safety glass films or equivalents Regarding the use of the molding material as an intermediate layer (adhesive film) in safety glass Ru.

To produce laminated safety glass, plastics with a moisture content of 0.2-0.8% by weight are used. Tempered (softened) PVB films are said to be particularly advantageous. polyviny The rubyral resin contains 10 to 28% by weight of vinyl alcohol units, advantageously 15 to 28% by weight of vinyl alcohol units. It is characterized by a proportion of 23% by weight. plasticized polyvinyl butylar The plasticizer content of the polyvinyl butyral resin is from 20 to 100 parts by weight of the polyvinyl butyral resin. 60 parts by weight, preferably 33 to 44 parts by weight.

Laminated safety glass is 0 laminated glass which is widely popular in the fields of vehicles and architecture. The requirements placed on boards are extremely wide-ranging. In the end, the product was made of laminated glass plate. For quality and safety, plasticized glass, which is made by bonding two or more glass sheets together as an interlayer, is important for quality and safety. The chemical-physical properties of the molded polyvinyl butyral bodies are decisive. Inside this The interlayer provides good impact strength to the laminated glass and protects the glass from collisions. It has the task of joining the pieces with good adhesion.

Besides these mechanical properties, the interlayer has high transparency, light fastness, moisture resistance and Aging properties (adhesion stability) must be guaranteed.

Plasticized polyvinylbutylene utilized as interlayer for laminated safety glass Ral films generally have glass adhesion forces that are too high for vehicle manufacturing. Flo The glass remains intact during an impact, while at the same time converting the impact into an energy absorber. For better inhibition, adhesion must be optimized.

level of technology Various alkali metal or alkaline earth metal compounds, such as hydroxides, salts, It is known that adding it in the form of a complex reduces the glass adhesion of the film. (West German Patent Application Publication No. 1596902, West German Patent Application Publication No. 159689) Specification No. 4, U.S. Patent No. 3,249,488, U.S. Pat. No. 3,249,489 , Specification No. 3262835, Specification No. 3262836).

The disadvantage of these alkaline-reactive compounds is that plasticized polyvinyl butyral This is due to the chemical changes in the resin, which makes the polyvinyl butyral/plasticizer system toxic. As discoloration due to and turbidity of the resulting laminated safety glass due to insufficient moisture resistance appear. Discoloration and clouding degrade the clarity of laminated safety glass. Furthermore, Al Other consequences of potashity include changes in the molecular size of the polymer, such as molecular weight and molecular weight. Fabric ratio and aging resistance change. Adhesion strength decreases when the peripheral area of the film absorbs moisture. However, peeling of the film from the glass occurs.

Therefore, in plasticized polyvinyl butyral films, it is difficult to influence adhesion. The use of silane as a substance that gives No. Publication, West German Patent No. 24101534) Specification, West German Patent Application Publication No. 265 However, all the silanes proposed so far have poor adhesion properties. exhibits incomplete reproducibility. Hydrolyzed during film manufacturing by mass production Condensation and network products resulting from silanes are visible to the naked eye in small areas within the film. Although it can be recognized as a nodule, it is of a quality and filtration suitable for the requirements of laminated safety glass. This eliminates reproducible adhesion adjustment to the glass of the film, thus making it difficult to The use of these products has hitherto been unsuccessful.

Invention problem The object of the present invention is to use silanization as an additive for adjusting adhesion, which does not have the above-mentioned disadvantages. partially acetalized polyvinyl alcohol containing a plasticizer for producing film-based laminated safety glass films or equivalents. The purpose was to provide molding materials.

Description of the invention The above-mentioned problem is to solve the above problem by using the general formula (I) as a silane compound: R'-(0-R'+mo- R6-3i RIR2(-0-(R'-0+mR') [in the formula, R1 and R2 each, independently of each other, contain from 1 to 4 carbons, optionally branched. an alkyl group or formula having an elementary atom; % formula % (13 represents a group shown by Each R3 is an optionally branched alkyl group having 1 to 4 carbon atoms. represents a hydrogen atom or a hydrogen atom, in which the groups R3 may be the same or different. , Each R4 is an optionally branched alkyl group having 2 to 4 carbon atoms. represents a ren radical, in which the radicals R4 may be the same or different, and R5 is represents an alkylene group having 1 to 6 carbon atoms, and m each independently represents a number from O to 16] Solved by using

The organosilane proposed according to the present invention surprisingly contains alkali metal compounds. or the advantages of alkaline earth metal compounds, i.e. reproducible adhesion control and known The advantages of silicon compounds, namely high transparency, avoidance of peripheral opacity and discoloration, Combine without showing its inherent drawbacks. This has been a huge expense for over 20 years. This was extremely unexpected since we had been searching in vain for the equivalent substance by spending a lot of time. .

R4 represents a linear alkylene group having 2 to 4 carbon atoms, in which case R 4 are the same, and R3 represents a linear alkyl group having 1 to 4 carbon atoms; death, o of formula (I) in which R5 represents a linear alkylene group having 2 to 6 carbon atoms; Preference is given to using luganosilane.

Advantageously, the radicals R1 and R2 each have the formula ni〇-(R4-○summR3 Groups that represent and are the same are equivalent.

More preferably, R4 represents an alkylene group having 2 carbon atoms (ethylene group). and R3 each represents a methyl group. Advantageously, m is in each case 3.

Suitable organosilanes according to the invention have the structure, for example: CH3-(OC2Ha)3-0- (CH2)3- S i -((OC2H4 )3-0-CH3)3-(methyltriethylene glycoxy)-pro Pirsilane-tris-methyltriethylene glycol ester, structure: 3-(methyltriethyleneglycoxy)-2-methylpro and lucilane represented by -tris-methyltriethylene glycol ester, structure: CH3-CH2-(OC2H4)3-0-(CH2)3-S　i　　C(O 3-(ethyltriethylene) represented by C2H4)3-0-C)12-CH3)3 glycoxy)-propylsilane-tris12tyltriethylene glycol ester le, structure: CH3 3-(ethyltriethyleneglycoxy)-2-methylpropylsilane represented by -tris-ethyltriethylene glycol ester, structure: CH3-(CH2)3- (OC2H4)3-0- (CH2)3-3 i-C (OC2H4)3-0- (CH2)3-CHs3s lyethylene glycoxy) - probylsilane - trisuptil triethylene glyco -Luester, structure: CH3-(OC2H4)3-0-(CH2)2-8 i-((OC2H4)3 -0-CH3)3 Lan-tris-methyltriethylene glycol ester, structure: CH3-(OC2H4)3-0-(CH2)4- S i ((OC2H4)3 -0-CHa's 4-(methyltriethylene glycoxy)-butyl lan-tris-methyltriethylene glycol ester, structure: CH3-(OC2H4)4-0-(CH2)3- S i -((OC2H4) 3-(Methyltetraethyleneglycoxy)-propylene represented by 4-0-CH3)3 Pirsilane-tris-methyltetraethylene glycol ester, structure: CH3-(OC2H4)! -0-(CH2)3-81-((OC2H4)s-0 -CHa]a 3-(methylpentaethylene glycoxy)-propyl lan-tris-methylpentaethylene glycol ester, CH3(OC2H4)30 CH2S i (CH3) ((OC2H4)3- St-methyl-(methyltriethylene glycoxy)-mer represented by OCH3)2 thyl-bis-methyltriethylene glycol ester, CH3 (OC2H4) 30 CH2S i (CH3) 2 (OC2) (4) 30 Si-3i-dimethyl-(methyltriethylene glycoxy) represented by CH3 )-methyl-methyltriethylene glycol ester.

Particularly advantageously, the silane has the structure: CH3-(OC2H4)3-0-(CH2)s-3t-((OC2H4)3-O 3-(methyltriethyleneglycoxy)-propylsilane represented by CH3)3 -tris-methyltriethylene glycol ester.

Organosilane with this structure is known from West German Patent No. 2,652,719 in a hydraulic system. It is well known as an additive to liquids used in storage. Regarding its manufacture, please refer to the specification and German Patent Publication No. 3908792 (earlier application by Huelg) German Patent J13908792゜1 Specification, March 17, 1989, Title: Unpaired Process for the preparation of generic, terminally unsaturated glycol ethers (Verfahren) zur Herstellung unsymmetrischer, end staendig einfach ungesaettigter Glyk olether)] and Specification No. j13908791 [earlier Huels ( West German Patent No. 3908791.3 of Huels, March 1, 1989 7th, Name: Method for producing silicon organic compounds (Verfahren zur Herr stallung van siliciumorganschen Ver. (bindungen)).

Preferably, one or more organosilanes according to the invention are incorporated into a plasticizer-containing polymer. Mix homogeneously.

Surprisingly, the silane according to the invention can be applied to plasticized polyvinyl butyral. A very small amount of 0.003 to 0.8% by weight can achieve the desired adhesion adjustment effect. It turned out that it shows.

The silicon and organofunctional silane are advantageously dissolved in a plasticizer (optionally dispersed) and together with the polymer in a known manner in a calender or in an extruder, Advantageously, films with a thickness of 0.3 to 1.5 mm are processed (see European Patent Application No. 0). 185863, British Patent No. 1271188).

As plasticizers, polyhydric acids, polyhydric alcohols or Esters of oligoether glycols, such as di(2-ethylhexyl)azi pate, dihexyl adibate, dibutyl sepasate, dioctyl phthalade, Linear or branched aliphatic carboxylic acids and di-, tri- and tetraethylene glycols Esters with coals as well as mixtures of these plasticizers are suitable. Phosphate ester A plasticizer mixture with polyvinyl butylene having a relatively high vinyl alcohol unit Used in cases where the

As plasticizers according to the invention, in particular aliphatic diols and long-chain aliphatic carboxylic acids are used. esters with, especially triethylene glycol and fats with 6 to 10 C* molecules Esters with group carboxylic acids such as 2-ethylbutyric acid and heptanoic acid are used. Ru. The plasticized polyvinyl butyral preferably contains from 24 to 32% by weight of plasticizer. Contains.

However, in addition to blending silane into plasticized polyvinyl butyral, This method improves the wetting of the silane on the film without compromising the film properties. Apply to the film surface by an appropriate method (spraying, dipping, printing) in a solvent containing You can also do that. As solvents, aromatic compounds, esters, chlorohydrocarbons and phase Corresponding non-polar solvents are suitable.

Similarly, silane diluted in a solvent can be plasticized when making laminated safety glass. It can be applied to the surface of the glass plate facing the polyvinyl butyral.

Generally, the silane concentration is 0°003 for plasticized polyvinyl butyral. ~0.8% by weight, an advantageous and often sufficient amount being 0.003-0.3% by weight, Very preferably from 0.01 to 0.1% by weight.

Polyvinyl acetal is acetalized from hydrolyzed polyvinyl ester. Manufactured by Examples of aldehydes include formaldehyde, acetal Dehyde, propionaldehyde, butyraldehyde, valeraldehyde and , preferably butyraldehyde. polyvinyl The carboxyl group of the ester belongs to fatty acids with 1 to 8 CIN children and is advantageous In this case, the group is an acetate group. Polyvinyl acetal has an acetyl group of O~2 0% by weight, preferably 0.5-3.0% by weight.

Advantageously, partially butyralized polyvinyl alcohol (PVB) is used. do.

As polyvinyl butyral resin, polyvinyl butyral resin that can be thermoplastically molded is used as a general rule. Any tyral resin can be used. Preferably vinyl alcohol units A resin containing 15-23% by weight is used.

The moisture content of the film should be adjusted to 0.2-0.8% by weight.

In an advantageous method for producing laminated safety glass, the film according to the invention inserted between glass plates of the same or different thickness, and at 60 to 100℃. Pressure is applied to the initial laminated glass. The final bonding is carried out for example in an autoclave at 120 It is carried out at ~160[deg.] C. and 8-16 bar with a pressure time ranging from 10 to 30 minutes.

In the experiments described in the examples below, we investigated the breaking strength of laminated safety glass, the hardness of the film, and The following test method was conducted to evaluate the color and peripheral opacity of the material: Impact strength. was tested based on ANSL 26.1-1983.5.26 Test 26. 23 A 30×30 cm laminated glass plate tempered at ℃ was placed horizontally in the frame.

A 2.26 kg steel ball was freely dropped from above into the center of a laminated glass plate. this experiment The falling height was varied, and 8 out of 10 samples were destroyed by the steel ball. The height of the drop was confirmed. Record the distance from the glass surface to the ball as the ball fall height. I will post it. The higher the falling height, the higher the breaking strength of the laminated safety glass.

Using a spectrum measuring device, model Labscan 5100, the yellowness coefficient (ΔYl is the difference between the measured value of laminated safety glass and the measured value of glass without film. ) was measured based on ASTM-D-1925 (glossy formula C, 2° observation) . The Δb values listed correspond to Yl of ASTM-D-1925.

Peripheral opacity, which affects adhesion stability and transparency, is defined by ANSL 26.1-1. 977, ring 5.3. Evaluated by Test 3, how much of the surrounding area became cloudy at that time? The width was measured to see if it could penetrate inside the laminated safety glass.

How to carry out the invention Example 1 Tinuvin F' (lightfast agent) for each plasticizer connotation.

C1ba (Geigy) 0.7% by weight and 3-(methyltriethylene glyco xy)-propylsilane-tris-methyltriethylene glycol ester 0. 14~0゜21% by weight dissolved, vinyl alcohol unit content 20.5% by weight. 72% by weight of polyvinyl butyral resin and triethylene as plasticizer Recall di-n-hebutanoic acid ester 28% by weight, European Patent Publication No. 0185 Based on the specification of No. 863, it was extruded into a film with a thickness of 0°76 mm and after air conditioning. Float glass with a thickness of 2.2 mm adjusted to an average moisture content of 0°45% by weight. was used to create laminated safety glass.

Example 2 A laminated glass plate was produced as in Example 1, but in this case the silane 2-(Methyltriethyleneglycoxy)-ethylsilane-tris-methyltrie The ratio of tyrene glycol ester to the plasticizer component is 0.14 to 0.21% by weight. used in the case.

Example 3 A laminated glass plate was produced as in Example 1, but in this case the silane , 4-(methyltriethyleneglycoxy)-butylsilane-tris-methyltri Ethylene glycol ester in an amount of 0.14 to 0.21% by weight based on the plasticizer component. used in proportion.

Comparative example 4 carried out as in Example 1, but in this case replacing the silane according to the invention. 10% by weight aqueous potassium acetate solution was used at 4.6% by weight based on the plasticizer component. did.

Comparative example 5 carried out as in Example 1, but in this case replacing the silane according to the invention. In addition, isobutyl-trimethoxysilane was used as described in West German Patent No. 2410153. was used in an amount of 1 to 1.8% by weight, based on the plasticizer component.

Continue to apply ANSI 26, l-1983 to the laminated glass corresponding to experiments 1 to 5. A ball drop test was conducted (Table 1).

Table 1 Additives Additives m! ! + Falling height m) Weight % --- 111111 beginning of year mid year Potassium acetate 0.13 5.25 5.50 0.4 3.50 L75 0.5 4.25 3.25 MTG-Silane I Q, 04 5.25 5.25MTG-Silane 1 0.05 5.50 5.50MTG-silane l O,065,505,75MTG-silane Run” 0.04 5.50 5.25MTG-Silane 2 (1-O55,25 5,50MTG-silane 2 0.06 5.50 5.50MTG-silane 3 0.04 5.25 5.25MTG-Silane 3 0.05 5.50 5.2 5MTG-silane 30.06 5.25 5.251) 3-(methyltriethyl (lene glycoxy)-propylsilane-tris-methyltriethylene glycol Stell 2) 2-(methyltriethyleneglycoxy)-ethylsilane-tris- Methyl triethylene glycol ester 3) 4-(methyltriethyleneglycoxy)-butylsilane-tris-methyl triethylene glycol ester 4) Silane loading expressed as ball fall height relative to the total amount of polymer/plasticizer mixture The adhesion-reducing effect and the optical purity of the film (nodules) are significantly reduced by the silane according to the invention. Based on the present invention, the invention is shown to be suitable and reproducible only in The reproducibility of the breaking strength (>4 m) suitable for the requirements for silane is appears in laminated glass sheets manufactured at different times (beginning and middle of the year). Ru.

Yellowness coefficient (ASTM-D-1925”) and peripheral opacity (ANSI26.1- 1977) are summarized in Table 2.

Table 2 Additive concentration Surrounding turbidity Surrounding humidity Weight% ΔYI Δb (!!l) Turbidity characteristics Potassium acetate 0.13 3.35 1.85 8 Robust (as a comparative example) MTG-Silane' 0.04 1.80 1.06 2 MT disappears within 14 days G-silane l O,051,901,112MTG-silane l O,061,7 31,012MTG-Silane 2 0.04 1.85 1.10 2MTG-Si Run 2 0.05 1.80 1.05 2MTG-Silane 2 0.06 1. 90 1.15 2MTG-Silane 3 0.04 1.75 1.02 2MT G-silane 3 0.05 1.82 1.07 2MTG-silane 3 0.06 1.88 1.13 21) 3-(methyltriethylene glycoxy)-pro Pyrsilane-tris-methyltriethylene glycol ester 2) 2-(methylene glycol ester) tris-methyltriethylene glycoxy)-ethylsilane-tris-methyltriethylene glycoxy coal ester 3) 4-(Methyltriethyleneglycoxy)-butylsilane-tris-methylt Liethylene glycol ester Example 6 Films and laminated safety glass were produced corresponding to Example 1, but with the exception that the plasticizer and triethylene glycol di-n-hebutanoic acid ester. Glycol-di-meiheptanoic acid ester was used.

The results are listed in Table 113 and Table 4.

Table 3 Potassium acetate 0.12 5.25 5.50 Table 4 Additive concentration Surrounding turbidity Surrounding humidity Weight % ΔYI Δb (dish) Turbidity characteristics Potassium acetate 0.12 3.34 1 ．． 85 6.5 Robust (as a comparative example) MTG-Shin5in” 0.04 2.08 1.20 2 MT disappears within 14 days G-silane 1 0.05 2.17 1.26 1.5MTG-silane 1. 0 ．． 06 2.09 1.21 1MTG-Silane 2 0.04 2.11 1. 24 1.5MTG-Silane 2 0.05 2.02 1.18 1MTG-Silane Run 2 0.06 2.06 1.22 1MTG-Silane 3 0.04 2. 15 1.26 1MTG-Silane 3 0.05 2.10 1.22 1MT G-silane 3 0-06 2.12 1.24 1.51) 3-(methyl tri ethylene glycoxy)-propylsilane-tris-methyltriethylene glycol ester 2) 2-(methyltriethylene glycoxy)-ethylsilane-tri Su-methyltriethylene glycol ester 3) 4-(methyltriethyleneglycoxy)-butylsilane-tris-methyl triethylene glycol ester international search report international search report EP 9000462

Claims (11)

[Claims] 1. Plasticized, partially with silane compounds as additives to adjust adhesion Acetalized polyvinyl alcohol, especially polyvinyl butyral (PVB) ) based on laminated safety glass films or equivalents. In, as a silane compound, - general formula (I) R3-(O-R4)-m O-R5-SiR1R2[-O-(R4-O)-mR 3] [In the ceremony, R1 and R2 each independently have 1 to 4 carbon atoms, optionally branched Represents an alkyl group or formula: -O-(R4-O)-mR3 represents a group shown by R3 each optionally represents a branched alkyl group having 1 to 4 carbon atoms; , in which the radicals R3 may be the same or different, R4 each optionally represents a branched alkylene group having 2 to 4 carbon atoms; but in this case the groups R4 may be the same or different, R5 optionally represents a branched alkylene group having 1 to 6 carbon atoms and m each independently represents a number from 0 to 16] A molding material for producing films for laminated safety glass, characterized in that it is used. 2. - In general formula (I) R4 represents a linear alkylene group having 2 to 4 carbon atoms, in which case the group R4 are the same, R3 represents a linear alkyl group having 1 to 4 carbon atoms, Claim 1, wherein R5 represents a straight-chain alkylene group having 2 to 6 carbon atoms. Molding material. 3. - In general formula (I) R1 and R2 each have the formula: -O-(R4-O)-mR3 The molded material according to claim 1 or 2, which represents a group represented by and is the same as each other. fee. 4. - In general formula (I), R4 is an alkylene group having 2 carbon atoms (ethyl 4. The molding material according to any one of claims 1 to 3, which represents a ren group. 5. - In the general formula (I), each R3 represents a methyl group, and each m is 3; A molding material according to any one of claims 1 to 4. 6. a) Structure: CH3-(OC2H4)3-O-(CH2)3-Si-[(OC2H4)3-O 3-(methyltriethyleneglycoxy)-ethylsilane- represented by CH3]3 tris-methyltriethylene glycol ester, b) structure; CH3-(OC2H4)3-O-(CH2)2-Si-[(OC2H4)3-O 2-(methyltriethyleneglycoxy)-ethylsilane represented by -CH3]3 -tris-methyltriethylene glycol ester and c) Structure: CH3-(OC2H4)3-O-(CH2)4-Si-[(OC2H4)3-O 4-(methyltriethyleneglycoxy)-butylsilane represented by -CH3]3 -One or more members of the group consisting of tris-methyltriethylene glycol esters A molding material according to any one of claims 1 to 5, in which the silane is used. 7. The silane was added to the plasticized polyvinyl butyral from 0.003 to 0. 8% by weight, advantageously up to 0.3% by weight, in particular from 0.01 to 0.1% by weight. A molding material according to any one of claims 1 to 6. 8. The polyvinyl butyral resin advantageously comprises 10 to 28% by weight, based on the polymer. Claims 1 to 7 have a vinyl alcohol unit proportion of 15 to 23% by weight. The molding material according to any one of the above. 9. Plasticizer-containing polyvinyl butyral resin is and having a plasticizer content of about 15 to 45% by weight, preferably 24 to 32% by weight. Molding material according to any one of ranges 1 to 8. 10. Claims for the use of extruded film as an interlayer in laminated glass sheets The molding material according to any one of items 1 to 9. 11. Two or more sheets of glass made of plasticized, partially acetalized polyvinyl using a plasticizer film based on alcohol, especially polyvinyl butyral. At the same time, the adhesion between the board and the plasticizer film is adjusted. Applying additives to the glass surface and/or film surface and/or applying the film In the manufacturing method of laminated safety glass, which is adjusted by adding Orga according to any one of claims 1 to 6 as an additive for adjusting force A method for producing laminated safety glass characterized by using nosilane.