JPS6114243A - Resin composition for interlayer of laminated glass - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent transparency, adhesiveness, and viscoelasticity by adding dibenzylidenesorbitol and a triphosphate in a small amount as a mixed melt to an ionomer resin, followed by adding the remainder thereto. CONSTITUTION:A mixed melt of dibenzylidenesorbitol and a triphosphate and/or a phosphonate in an amount of 0.03-0.45pt.wt. in terms of dibenzylidenesorbitol and 0.5-40.0pts.wt. triphoshate and/or phosphonate are incorporated into 100pts. wt. ionomer resin having a haze value of 35% or lower. If the haze value of the ionomer resin exceeds 35%, that of the obtained interlayer composition will be unfavorably high, causing blushing. The example of a triphosphate or a phosphonate to be used includes triethyl phosphate, octyl diphenyl phosphate or 2-ethylhexyl phosphonate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for a laminated glass interlayer film, and more specifically, an ionomer resin having a haze value of 35% or less as specified in ASTM D 1003, dibenzylidene sorbitol, triphosphate, and A laminated glass with excellent properties such as transparency, adhesiveness, and appropriate viscoelasticity of the film, which is made by blending a blended product of phosphonic acid ester, triphosphoric acid ester, and/or phosphonic acid ester in a specific ratio. The present invention relates to a resin composition for interlayer films.

Laminated glass, which is obtained by sandwiching an interlayer film for laminated glass between two glass plates and applying heat and pressure, is used today in automobiles,
Widely used for window glass of aircraft, high-rise buildings, etc.

Conventionally, polyvinyl butyral (PVB), which has been commonly used as a material for interlayer films for laminated glass, requires advanced technology and complicated processes to manufacture, is economically expensive, and is difficult to apply to glass. A special adjustment process is also required during lamination and pressure bonding, and laminated glass using this interlayer film has the drawback of peeling and whitening at the edges due to moist heat or rapid temperature changes.

Various researches have been conducted on new thermoplastic resin materials to replace PVB, and many patent applications have been filed, but no polyolefin material has yet been put into practical use. Among polyolefin materials, ionomer resin, which has particularly excellent transparency and toughness, is highly suitable as an interlayer film material, and various applied researches have been conducted in the past.For example, the invention disclosed in Japanese Patent Publication No. 13267/1983 Although the amount of neutralization of salt was adjusted to balance glass adhesive strength and transparency, elasticity and strength were not sufficient.

Special Publication No. 54-949 and Special Publication No. 52-2367
The invention disclosed in Publication No. 3 is an attempt to improve the suitability of ionomer resins by designing the molecular structure of multi-component copolymerized ionomer resins. It hasn't arrived yet. The basic properties required for materials such as interlayer films for laminated glass are transparency and adhesion, as well as appropriate viscoelasticity of the film.

The fundamental reason why ionomer resins cannot be put to practical use as interlayer films lies in the unresolved third fundamental property, specifically the unresolved technology for imparting flexibility and toughness to films.

We have investigated various alternatives using polyolefin materials (including original polyolefin resins and copolymer resins containing 50% or more of polyolefin resin) that can match the performance of P V B interlayer films, but With polyolefin resin, it is difficult to adjust the adhesion strength to the glass, and it is difficult to balance the properties of anti-penetration and safety performance, but the transparency is low and the phenomenon of blurring and fogging is likely to occur.

In addition, there are few products with satisfactory light resistance, heat resistance, and moisture resistance.
Fluidity (glass pressure bonding process is low 1, moldability, dimensional stability + around 100℃! [IJ i'fi is 66, even 1 minute
A suitable material could not be obtained due to various disadvantages such as distortion in visible light transmission due to unevenness of the blended ingredients, which was less than 2°, and lack of flexibility of the material.

Among them, the interlayer film composition for laminated glass disclosed in JP-A-59-69448, which has a particularly high suitability for ionomer resins with a specific structure and contains 1 to 10% by weight of a specific alkaline earth metal. The material has particularly good optical properties after glass lamination. However, this interlayer film composition also suffers from poor moldability, dimensional stability, and film flexibility at room temperature due to the influence of polyethylene, which is the main component of the ionomer resin, and when used as an interlayer film. The strength of rigidity was the main reason for the lack of balance in order to achieve anti-penetration safety performance.

The present invention was made in order to overcome the problems of the prior art, and provides a resin composition for interlayer film of laminated glass that has excellent properties such as transparency, adhesiveness, and appropriate viscoelasticity of the film. Especially for automobile windshields,
``Used as an interlayer film for window glass of high-rise buildings, etc.

As a result of studies in line with the above objectives, the present inventors focused on Japanese Patent Application No. 49204, which improves the moldability, dimensional stability, and flexibility of polyolefin materials, and found that the dibenzylidene used therein It has been discovered that a mixed product of sorbitol and triphosphate and/or phosphonate is effective in modifying ionomer resins and is extremely effective in imparting impact-reducing effects as an interlayer film for laminated glass. did. That is, in order to make the ionomer resin exhibit suitability as an interlayer film, a small amount of a mixed product of dibenzylidene sorbitol and a triphosphoric acid ester and/or a bosphonic acid ester is added, and then the ester component of the mixed product is added. It has been found that a method of adding an ester of the same type as a plasticizer is effective, and the present invention has been achieved.

That is, in the present invention, 100 parts by weight of an ionomer resin having a haze value of 35% or less, a mixed product of dibenzylidene sorbitol and triphosphate d3 and/or phosphonate, with a dibenzylidene sorbitol content of 0
．． 03 to 0.45 parts by weight, Nisdel triphosphate J) and/or 0.5 to 40.0 parts by weight of phosphonic acid ester.

In the present invention, an ionomer resin having a haze value defined by ASTM D 1003 of 35% or less is used. If the haze value of the ionomer resin exceeds 35%, the resulting interlayer film composition will have a high haze value and a white side will appear, which is not preferable.

The ionomer resin referred to in the present invention is an ethylene/acrylic acid copolymer resin and/or ethylene/methacrylic acid copolymer resin crosslinked with metal ions, in which a portion of the acrylic acid and/or methacrylic acid has a metal ion. It has a structure in which the molecular chains are cross-linked by ions such as storium ions, potassium ions, lithium ions, zinc ions, magnesium ions, etc., and it has very strong characteristics at room temperature. When heated, the crosslinking force of metal ions is weakened, and it has the property of being moldable like general thermoplastic resins.

In the present invention, the triphosphoric acid ester and/or phosphonic acid ester forming the fused product with the dibenzylidene sol has a boiling point of 760 mm) to 210'
C or higher is preferable, but there are further restrictions on the molecular shape from the viewpoint of maintaining optical properties.

The reason for this is that the triphosphoric acid ester and/or phosphonic acid ester used in the mixed product, the plasticizer, and the 1~lyphosphoric acid ester and/or phosphonic acid ester used in Considering the characteristics ↑1 of With the exception of some ates etc., they were used as plasticizers. In some cases, the compatibility with ionomer resins is low, and there are limits to the triphosphate and/or phosphonate that can be used as plasticizers. It should be noted here that the molecular shape of triphosphoric acid ester and/or phosphonic acid ester in the mixed product is not a factor in its disadvantageous compatibility with the ionomer resin.
, these 1 to lyphosphoric acid esters or phosphonic acid esters may be used alone or in combination of two or more.

The mixing ratio of dibenzylidene sorbitol and triphosphoric acid ester and/or bosphonic acid ester is not particularly limited, but considering the blending effect of the mixed product, a mixing ratio of 30 nia 0 to 70; 30 (weight ratio) is preferable. .

In the present invention, the fused product is blended in an amount of 0.03 to 0.45 parts by weight as dibenzylidene sorbitol to 100 parts by weight of the ionomer resin.

If the blending ratio of dibenzylidene sorbitol exceeds 0.45 parts by weight, a haze phenomenon occurs when a large amount is administered, which is thought to be caused by the benzene groups in the mixed product, while if it is less than 0.03 parts by weight, the blended product No mixing effect occurs. Further, the mixing temperature is preferably 60°C or higher -F to promote melting.

It is necessary to increase the amount of plasticizer in order to improve the normal stiffness of the ionomer resin, specifically the stress characteristics, to a range suitable for interlayer films, but this may cause problems such as transmittance, haze resistance, perspective distortion resistance, etc. In order to prevent this, the ester should be of the same type as the ester used in the blended product, and therefore the T stellate originally used in the blended product should also be avoided.

The desired stress property for an ionomer resin laminated glass interlayer is an initial 100% modulus of 100! ?
/ ci J, elongation must be 300% or more. Dirt lowers the initial modulus and has excellent flexibility and deformability.
It also means that the material has strong tenacity up to its breaking limit. Therefore, even if the lower limit of the initial 100% modulus is the effective limit of about 20 to 30 Kg/cIi, it is set as a Japanese-style room. The special performance of the room-temperature metal crosslinking of ionomer resins is reflected in this viscosity, but the rigidity of the polyethylene chains that form the main skeleton significantly affects the initial modulus. The membrane lacks the necessary flexibility.

In the present invention, by blending a plasticizer, that is, a triphosphate ester and/or a phosphonate ester, with the ionomer resin, the flexibility can be adjusted to the above stress characteristic range, but the amount of plasticizer blended and the safety glass It must be noted that there is no proportional correlation with the impact mitigation ability of .

In other words, the amount of plasticizer blended has an optimal value for each compounding system, but it does not exist unilaterally on the increasing side, but it depends on the coexistence of other compounding agents, glass adhesion strength, film thickness, and impact force. It should be set on balance. In the present invention, the blending amount of the plasticizer that satisfies the basic conditions of stress properties is within the range of 0.5 to 40 parts by weight, and the type and blending amount of the mixed product of dibenzylidene sorbitol, as well as the plasticizer. The value varies depending on the type of triphosphate and/or phosphonate used and the crosstalk conditions.

The triphosphate esters used here include 1-heliedyl phosphate, tributyl phosphate, octyl diphenyl phosphate, trioctyl bosphate, tributoxyethyl phosphate, etc., and the phosphonic esters include diptyl butyl phosphate, di(2- ethylhexyl) 2-ethylhexylphosphonate, 2-
(2) Derhexyl phosphoric acid mono-2-ethylhexyl ester is exemplified.

Hereinafter, the present invention will be specifically explained in detail based on Examples, Comparative Examples, and Reference Examples. Note that all formulation values in Tables 4 and 5 are parts by weight.

Reference Example 1 Triphosphoric acid esters and phosphonic acid esters a to 11 used in the mixed synthesis reaction with dibenzylidene sorbitol were added to the first
Shown in the table. In Table 1, the number of moles indicates the actual amount used in the reaction per 1 liter of dibenzylidene sorbitol (1 molecule 358). Dibenzylidene sorbitol was quantitatively measured into a reaction vessel, and a specified amount of Nisder triphosphate or phosphonic acid ester (hereinafter abbreviated as ester) was added, stirred thoroughly, the atmosphere was completely replaced with nitrogen, and heating was performed in stages. The temperature at which the reaction completed completely varied depending on the ester, and the higher the boiling point, the higher the temperature.
The temperature never exceeded 40°C. The mixed molten product was initially a brown transparent liquid, but upon slow cooling, it slowly solidified into a waxy state. The setting behavior was influenced by the type of ester and the number of reacted moles.

Reference Example 2 Table 2 shows the physical properties of the ionomer resin, its suitability when used as a bonding metal, a laminated glass interlayer film, and directions for improvement.

Among the ionomer resins A to N, haze value 35% is suitable as a material suitable for improving the interlayer film for laminated glass.
I selected the following: E, J, K, L, M, and N
Met. Ionomer resins with a haze value of more than 35% have a haze value of 0.8 ± 0 after addition of the fused product and increased m of plasticizer.
．． It was difficult to suppress the haze value to 1.5% or less after laminating an interlayer film of 0.4 mm' in thickness between two sheets of glass of 2-3 mm thickness.

As shown by the bending stiffness modulus or tensile impact value, there are cases where the stiffness and strength are strong, and cases where the stiffness is not significant but there is strong resistance to impact, and both are unsuitable as laminated glass interlayer film materials. It was necessary to improve flexibility.

Figure 1 shows the flexural rigidity and tensile impact values of ionomer resins A to N, and the dotted line indicates the improvement reference line for the flexural rigidity and tensile impact 7 values.
#i or less, tensile impact value 300Kg-cm/ct
It is necessary to bring it close to i. This standard is a value set as a barometer based on the physical properties of conventionally used PVB. In tensile impact 11 of 10 m/sec culm, the deformation behavior appears to be about 115 times more compressed than normal elastic deformation, so each elongation deformation, which is an important factor for safety, is examined based on the correlation with stress. This is an important function of a laminated glass interlayer film, and a suitable evaluation for this is performed by analyzing data on steady modulus, strength, and critical elongation.

However, it is always necessary to simulate data in consideration of the fact that each deformation appears compressed during an impact. From this point of view, if the critical elongation, such as low elongation modulus, is fundamentally important data, then 1'! I cut it off, 100%
A modulus (20% of the apparent modulus at high-speed impact) and a critical elongation of 300% or more (60% of the apparent critical elongation at high-speed impact) were considered to be the conditions required for the interlayer film. 'Taste-N +s3 Among the ionomer resins, ionomer resin was selected as an example of a resin with a high bending rigidity, and ionomer resin N was selected as an example of a resin with high tensile impact marks, and this ionomer resin was added to 100 parts by weight of N. Mixed product (1) ~
(14) A compatibility evaluation was conducted in the case where 0.5 parts by weight and 5.5 parts by weight of the same ester as the ester used in the mixed product as a plasticizer were added, and the results are shown in Table 3.

In the compatibility evaluation shown in Table 3, those in which 5 parts by weight or more of Nisdel were mixed were evaluated as good, and those in which Nisdel was not mixed in were evaluated as poor.

Examples 1 to 3 and ratio examples 1 to 3 The compositions shown in Table 4 were mixed for 1 hour at a roll gear ratio of 1:1.25 and a controlled temperature of 80±5°C to prepare interlayer film compositions for laminated glass. , the tensile strength for this interlayer film composition,
Elongation was carried out in accordance with JIS K6301, and a steel ball impact penetration test was also carried out.

The results of the tensile strength and elongation are shown in FIG. 2, and the results of the steel ball impact penetration test are shown in Table 4. In addition, the steel ball impact penetration test was 2.28 at 20-23℃.
A steel ball of Kg (51B) was dropped naturally from a height of 4.0m, and a 3051 square laminated glass LJIS 'R321 was created.
1) was tested to destroy it. In addition, the film cut shear in the steel ball m impact test refers to the shear crack caused by the glass breakage along the glass breakage.

Reference Example 4 An interlayer film composition for laminated glass was prepared using the ionomer resin, blended product, and ester shown in Table 5, varying the amount of ester blended, and the limit blending amount and preferred blending amount of each ester were determined. The results are shown in Table 5. In addition, in preparing the interlayer film composition, the roll gear ratio is 1:1.25.
, mixed for 1 hour at a controlled temperature of 80±5°C. This limit blending amount and preferred blending amount are influenced by the roll gear ratio, control temperature, kneading machine, etc., and when these are taken into consideration, the blending amount of ester is 0.0000 parts per 100 parts by weight of the ionomer resin.
It is 5 to 40.0 parts by weight.

As explained above, the combination of the present invention is a combination of a specific ionomer resin, a mixed product of dibenzylidene sorbitol and a triphosphate ester and/or a phosphonate ester, and a triphosphate ester and/or a phosphonate ester in a specific ratio. The resin composition for glass interlayer film satisfies the stress characteristic range of 100% modulus of 9/ci or less and elongation of 300% or more, and can be used in combination with a laminated glass interlayer film. As a result, the following effects are achieved.

■: An interlayer film for laminated glass made of ionomer resin, which is a cheaper material base than PVB, was obtained.

■2 Can be mass-produced using a regular plastic continuous molding machine.

■The viscoelastic properties of near-ionomer resins can now be adjusted over a wide range, making it possible to design materials that meet safety requirements.

■; Material with excellent moisture resistance and durability.

■No special adjustment process is required when laminating and crimp bonding.

[Brief explanation of the drawing]

Figure 1 is a graph showing the flexural rigidity and tensile impact value of ionomer resins A to N, as well as their improvement standard values, and Figure 2 is a graph showing the elongation and tensile strength of Examples 1 to 3 and Comparative Examples 1 to 3. A graph showing relationships.

Claims (1)

[Claims] 1. 100 parts by weight of an ionomer resin with a haze value of 35% or less, a mixed product of dibenzylidene sorbitol and a triphosphoric acid ester and/or a phosphonic acid ester, with a dibenzylidene sorbitol content of 0.03 to 0. .45
1. A resin composition for a glass interlayer film, which contains 0.5 to 40.0 parts by weight of a triphosphate ester and/or a phosphonate ester. 2. The triphosphate and/or phosphonate is triethyl phosphate, tributyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributoxyethyl phosphate, dibutylbutyl phosphate, di(2-ethylhexyl)
The resin composition for a laminated glass interlayer film according to claim 1, which is at least one selected from 2-ethylhexylphosphonate and 2-ethylhexylphosphoric acid mono-2-ethylhexyl ester.