TWI411636B - Plasticizer composition for polyvinylbutyral and polyvinylbutyral composition - Google Patents

Abstract

The present invention relates to a plasticizer composition for polyvinylbutyral and a polyvinylbutyral containing the same, said plasticizer composition comprises diethylene glycol dibutyl adipate represented by formula (I) and triethylene glycol di-(2-ethylhexanate) represented by formula (II): C4H9-(OCH2CH2)2-O-C(=O)-(CH2)4-C(=O)-O-(CH2CH2O)2-C4H9 (I) C4H9-CH(C2H5)-C(=O)-O-(CH2CH2O)3 -C(=O)-CH(C2H5)-C4H9 (II). The plastizer composition of the present invention is compatible with polyvinylbutyral so that it is suitable used as a plastizer for polyvinylbutyral having a wide range of hydroxyl group content.

Description

Plasticizer composition for polyvinyl butyral and polyvinyl butyral composition

The present invention relates to a plasticizer composition, and more particularly to a plasticizer composition of polyvinyl butyral.

A typical polyvinyl butyral film can provide a satisfactory mechanical property, adhesive properties, encapsulating properties, and film processability by a plasticizer. Therefore, polyvinyl butyral can be widely used in the manufacture of glued glass and can be applied to the automotive industry, the construction field, and the solar cell field.

In addition to the basic properties and safety of polyvinyl butyral as a sandwich of laminated glass, the plasticizer used in polyvinyl butyral film needs to be considered for compatibility and durability with polyvinyl butyral resin.

A plasticizer that is compatible with polyvinyl butyral resin is selected to avoid undesirable properties due to phase separation after processing.

The volatility and migration of the plasticizer have a great influence on the durability of the polyvinyl butyral film, and the volatility of the volatility in the processing of the autoclave is relatively high.

Since the content of hydroxyl groups contained in polyvinyl butyral is inversely related to the compatibility of the plasticizer, in view of the mechanical properties (impact resistance) of the film and the compatibility with the plasticizer, it is generally required to shrink the polyethylene. The hydroxyl group contained in the aldehyde is limited to a specific range. If it is outside this specific range, it is not compatible with too many plasticizers, and the obtained polyvinyl butyral film is high in volatility and therefore has no durability. When the plasticizer amount is too small, the polyvinyl butyral can not be effectively plasticized. At this time, the obtained polyvinyl butyral film will not dissipate the external impact force and balance the durability, and thus when polyvinyl butyral is used for the production of the bonded glass, the bonded glass will be adversely affected. Therefore, it is compatible with polyvinyl butyral and can obtain satisfactory impact resistance and durability, and is a condition required for a good plasticizer of polyvinyl butyral. In terms of plasticizer compatibility and durability, the hydroxyl content of the polyvinyl butyral must generally be limited to a certain small range, for example, to about 2 wt%.

Based on the above problems, the present inventors have desired a plasticizer suitable for a wide range of hydroxyl content of polyvinyl butyral, and thus extensively studied plasticizers for polyvinyl butyral, and found that specific ingredients are contained in a specific ratio. As a plasticizer, the aforementioned problems can be overcome, and thus the present invention has been completed.

The first object of the present invention relates to a plasticizer composition comprising di(butyl diethylene glycol) adipate and triethylene glycol di-(2-ethylhexanoate), wherein the adipic acid II The weight ratio of (butyl diethylene glycol) ester to the di-(2-ethylhexanoic acid) triethylene glycol ester is from 90:10 to 10:90.

The di(butyl diethylene glycol) adipate has the following chemical formula: C ₄ H ₉ -(OCH ₂ CH ₂ ) ₂ -OC(=O)-(CH ₂ ) ₄ -C(=O)-O -(CH ₂ CH ₂ O) ₂ -C ₄ H ₉ ; and the di-(2-ethylhexanoic acid) triethylene glycol ester have the following chemical formula: C ₄ H ₉ -CH(C ₂ H ₅ )-C (=O)-O-(CH ₂ CH ₂ O) ₃ -C(=O)-CH(C ₂ H ₅ )-C ₄ H ₉ .

When the plasticizer composition of the present invention uses a plasticizer as polyvinyl butyral, it has good compatibility with a polyvinyl butyral resin, whereby the formed polyvinyl butyral film can be excellent. Mechanical properties and low volatility.

A second object of the present invention relates to a polyvinyl butyral composition comprising 100 parts by weight of polyvinyl butyral and 20 to 50 parts by weight of the above-mentioned di(butyl diethylene glycol) adipate and a plasticizer composition of di-(2-ethylhexanoic acid) triethylene glycol ester; and wherein the di(butyl diethylene glycol) adipate and the di-(2-ethylhexanoic acid) three The weight ratio of ethylene glycol ester is from 90:10 to 10:90.

The polyvinyl butyral to which the plasticizer composition of the present invention is applicable may have a hydroxyl group content of 15 to 30% by weight, preferably a hydroxyl group content of 15 to 25 % by weight and preferably 18 to 23% by weight.

The invention provides a plasticizer composition comprising di(butyl diethylene glycol) adipate and tris(2-ethylhexanoic acid) triethylene glycol ester, wherein the adipic acid di(butyl butyl) The weight ratio of the ethylene glycol) ester to the di-(2-ethylhexanoic acid) triethylene glycol ester is from 90:10 to 10:90, preferably from 30:70 to 70:30.

According to the present invention, the plasticizer composition of di(butyl diethylene glycol) adipate and di-(2-ethylhexanoic acid) triethylene glycol ester of the present invention has good properties with polyvinyl butyral. Since it has a compatibility and a low volatility, when the polyvinyl butyral hydroxyl group content is in a wide range, a polyvinyl butyral film excellent in physical properties such as mechanical strength can be obtained. For example, the polyvinyl butyral has a hydroxyl group content in a wide range of 15 to 30% by weight, and the use of the present invention of di(butyl diethylene glycol) adipate and di-(2-ethylhexanoic acid) triethyl Under the plasticizer composition of the glycol ester, a polyvinyl butyral film having excellent mechanical strength and high temperature and low volatility can be obtained.

The present invention further provides a polyvinyl butyral composition comprising 100 parts by weight of polyvinyl butyral and 15 to 55 parts by weight of the plasticizer composition of the present invention; wherein adipic acid di(butyldiethylene) The weight ratio of the alcohol ester to the bis-(2-ethylhexanoic acid) triethylene glycol ester is from 90:10 to 10:90, more preferably from 70:30 to 70:30.

More preferably, the polyvinyl butyral composition comprises 100 parts by weight of polyvinyl butyral and 20 to 50 parts by weight of the plasticizer composition of the present invention; preferably, the polyvinyl butyral composition comprises 100 parts by weight. Polyvinyl butyral and 30 to 45 parts by weight of the plasticizer composition of the present invention.

The preparation of polyvinyl butyral used in the present invention can be carried out by subjecting a polyvinyl alcohol having an average degree of polymerization of from about 800 to 3,000, preferably an average degree of polymerization of from about 1,000 to about 2,500, to butyraldehyde in the presence of a catalyst. It is well known to those skilled in the art and is not intended to limit the scope of the invention.

The polyvinyl butyral used in the present invention obtained by the above method has a hydroxyl group content of 15 to 30% by weight, preferably 15 to 25% by weight, preferably 18 to 23% by weight.

The polyvinyl butyral composition of the present invention may further contain other additives, and the additives are not particularly limited as long as they do not adversely affect the properties of the film produced from the composition. Non-limiting examples thereof include, for example, ultraviolet absorbers such as benzotriazole series, Tinuvin. RTM. 326, Tinuvin. RTM. 320, Tinuvin. RTM. 328, manufactured by Ciba-Geigy; adhesion control agents such as alkali metals or Alkaline earth metal formate, acetate, such as potassium formate, potassium acetate, magnesium formate, magnesium acetate, sodium formate, sodium acetate, etc.; antioxidants such as antioxidant A050 and antioxidant A060 produced by Changchun Petrochemical; and light stabilizers, etc. .

The invention will be described in more detail in the following examples and comparative examples. These examples are for illustrative purposes only and are not intended to limit the scope of the invention. Various modifications and adaptations will be apparent to those skilled in the <RTIgt; Such modifications and adaptations are within the scope of the invention without departing from the spirit and scope of the invention.

In the following examples and comparative examples of the present invention, the following method is used to determine the di(butyl diethylene glycol) adipate and the di-(2-ethylhexanoic acid) triethylene glycol ester of the present invention. The physicochemical properties of the plasticizer composition and the film properties obtained by blending the obtained plasticizer with polyvinyl butyral.

A, fog point (compatibility): 5.6 g of polyvinyl butyral resin was dissolved in 70 g of plasticizer and heated to 150 ° C to form a clear solution, slowly cooled and recorded the temperature at which the solution began to white fog, this The temperature is the fog point. The lower the fog point, the better the compatibility of the two components.

B. Hydroxyl content of polyvinyl butyral: Measured by the method described in JIS K6728. 0.4 g of polyvinyl butyral was accurately weighed in a capped triangular flask, and 10 ml of a pyridine-acetic anhydride solution was added. The mixture was refluxed for 2 hours with a reflux condenser. After cooling, 20 ml of 1,2-dichloroethane was added over the condenser. After thorough stirring, 50 ml of deionized water was added and mixed uniformly, and allowed to stand for 30 minutes. The drop of 3 drops of phenolphthalein indicator was titrated with 0.5 N NaOH until the appearance of reddish color. Record the number of milliliters (a) of 0.5 N NaOH titration. A blank test was also performed and the number of milliliters (b) of 0.5 N NaOH titration was recorded. The hydroxyl content is calculated by the following formula:

Hydroxyl wt% = (b-a) * f * 220.25 / sample weight

Where f is 0.5N NaOH factor (factor)

Preparation Example 1: Preparation of polyvinyl butyral

1000 kg of polyvinyl alcohol having a polymerization degree of 1700 and a saponification value of 98.5 mole% was added to 9000 liters of water to be dissolved by heating, and the solution was cooled to 16 ° C, and 115 kg of 35 wt% hydrochloric acid and 590 kg of butyraldehyde were added for condensation reaction, and the reaction was maintained at 16 °C until the polyvinyl butyral precipitated. Then the temperature was raised to 60 °C. The reaction mixture was maintained at 60 ° C for 3 hours with stirring to complete the reaction. The polyvinyl butyral precipitate was washed with deionized water and dried in a desiccator to obtain a polyvinyl butyral having a hydroxyl group content of 17.4% by weight.

Preparation Example 2: Preparation of polyvinyl butyral

Following the same procedure as in Example 1, except that 550 kg of butyraldehyde was used in place of the amount of butyraldehyde of Example 1, a polyvinyl butyral having a hydroxyl group having a hydroxyl group content of 21.8 wt% was obtained.

Example 1-12

5.6 g of polyvinyl butyral from Preparation Example 1-2 was blended with 70 g of a plasticizer to obtain a blend, and the plasticizer was di(butyl diethylene glycol) adipate and di-(2- Ethylhexanoic acid) Triethylene glycol ester was a mixture of the ratios shown in Table 1, followed by a fog point test of the blend, and the results are shown in Table 1.

Comparative Example 1-2

The 5.6 g of the polyvinyl butyral from Preparation Example 1-2 was subjected to the above-mentioned haze test as described above with 70 g of the dihexyl oxalate (DHA) plasticizer, and the results are shown in Table 2.

The results of Tables 1 and 2 show that the composition of di(butyl diethylene glycol) adipate and the triethylene glycol diethylene glycol adipate of the present invention and polyvinyl butyral The compatibility of the resin is better than DHA. The better compatibility means that the phase separation is less likely to occur after processing into a film, resulting in poor properties.

Examples 13-17 and Reference Example 1

Examples 13-17 and Reference Example 1 used 100 parts by weight of the polyvinyl butyral resin prepared in Preparation Example 2 in the order of the plasticizer compositions shown in Examples 7-12 (see Table 3). The parts by weight are mixed in a high intensity mixer. The plasticized heterogeneous polyvinyl butyral mixture is melted in an extruder and forced through the die forming the film. The melt temperature was about 195 ° C and extruded into a polyvinyl butyral sheet of about 0.76 mm.

The prepared polyvinyl butyral sheet was placed between two sheets of flat glass (30 cm long * 30 cm wide * 3 mm wide). The glued glass was placed in a rubber bag and evacuated, and the vacuum was maintained at 20 Torr for 10 minutes to remove air. The vacuum was maintained at a temperature increase rate of 5 ° C/min to 100 ° C. After cooling, the glued glass was taken out. The glued glass was placed in an autoclave. The autoclave temperature was raised to 130 ° C and the pressure was raised to 13 kg / cm 2 for 30 minutes. After the autoclave temperature was cooled to below 50 ° C, the pressure was released to prepare a finished glued glass.

The tensile strength, compatibility, and thermogravimetric loss rate of the polyvinyl butyral film were measured by the following methods. The edge dimensional stability and penetration resistance test of the produced glued glass was measured by the following method. The results are shown in Table 4.

A. Tensile strength: A test piece was prepared according to the method of ASTM D412. The polyvinyl butyral film was kept at 20.6 ° C and a relative humidity of 23.5% for 48 hours before the test. The test piece was tested at a tensile speed of 200 mm/min using a universal testing machine. The tensile strength at which the test piece was broken was recorded.

B. Compatibility: The polyvinyl butyral film is sandwiched between two sheets of blotting paper and placed in a relative humidity of 100% and 0 °C for 72 hours. Observe whether the plasticizer oozes out of the blotting paper. If it oozes, it means no plasticizer. Compatible, and vice versa.

C. Thermogravimetric loss rate: The polyvinyl butyral film was placed in an oven at 160 ° C for 1 hour and 2 hours, and the heat loss rate of the film was measured.

D. Edge size stability: The prepared glued glass was placed in an environment of 80 ° C and a relative humidity of 95% for 2 weeks, and the distance of whitening of the edge of the bonded glass was observed.

E. Average ball drop height: 10 groups of 30*30 cm glued glass were kept at 21 ° C for 4 hours before the test. Use the electromagnetic ball drop tester to make 2.27 kg steel balls fall to the specified height and hit the impact glued glass on the support table according to CNS10986, R3117. Check whether the steel ball penetrates the glued glass. The test procedure is as follows:

1) Set the steel ball to a height of 5 meters, and drop the steel ball to hit the first set of glued glass; i) If the steel ball passes through the glued glass, the test result is recorded as unqualified; ii) If the steel ball does not penetrate the glued glass, it is supported On the glued glass, the test results are recorded as qualified;

2) After removing the glued glass from the support table and cleaning the broken piece, placing the next set of glued glass on the support table;

3) Raise the steel ball to the specified height. If the previous set of tests is qualified, the height of the falling ball is 0.25 meters higher than the height of the previous group. If the previous test fails, the height of the falling ball is 0.25 meters lower than the height of the previous set. And record the result as qualified or unqualified;

4) Repeat steps 2)~3) to test all 10 sets of glued glass;

5) Calculate the average ball drop height.

Comparative example 3

In the same manner as in Examples 13-17, 100 parts by weight of the polyvinyl butyral of Preparation Example 2 was blended with 38 parts of a plasticizer, but the plasticizer was changed to dihexyl oxalate (DHA) and two- (2-ethylhexanoic acid) triethylene glycol ester. The properties of the film and the bonded glass were tested as described above. The results are shown in Table 4.

As can be seen from Table 4, the polyethylene prepared by using the mixed plasticizer of di(butyl diethylene glycol) adipate and triethylene glycol di-2-ethylhexanoate of the present invention in Examples 13-17 The butyral film has a lower thermogravimetric loss rate than the comparative example 3 using only DHA as a plasticizer and Reference Example 1 using only bis-(2-ethylhexanoic acid) triethylene glycol ester as a plasticizer, which contributes to The safety and durability of the film processing and glass bonding process can be improved, and the bonded glass can achieve excellent penetration resistance and edge dimensional stability.

It can be seen from the data of Tables 1 and 4 that when only di(butyl diethylene glycol) adipate is used as the plasticizer in Example 1, although the fog point is low, that is, although it is reduced with polyethylene. The compatibility of butyraldehyde is better, but the average ball drop height of the obtained film is relatively low, indicating that the impact resistance is relatively insufficient. Therefore, the plasticizer composition of the present invention is sufficiently proved to be a plasticizer of polyvinyl butyral, which has good compatibility with polyvinyl butyral, and the impact of the polyvinyl butyral film thus obtained is impact resistant. Sexuality and edge size stability are good.

Claims (8)

A plasticizer composition for polyvinyl butyral comprising di(butyl diethylene glycol) adipate and triethylene glycol di-(2-ethylhexanoate) in a weight ratio of Di(butyl diethylene glycol) adipate: Tris-(2-ethylhexanoic acid) triethylene glycol ester is from 90:10 to 10:90. The plasticizer composition of claim 1, wherein the weight ratio of the di(butyl diethylene glycol) adipate: di-(2-ethylhexanoic acid) triethylene glycol ester is 70: 30 to 30:70. A polyvinyl butyral composition comprising 100 parts by weight of polyvinyl butyral and 15 to 55 parts by weight of a plasticizer composition as claimed in claim 1 or 2. A polyvinyl butyral composition according to claim 3, wherein the plasticizer composition is contained in an amount of from 30 to 50 parts by weight. A polyvinyl butyral composition according to claim 3, wherein the polyvinyl butyral has a hydroxyl group content of 15 to 25 wt%. A polyvinyl butyral composition according to claim 5, wherein the polyvinyl butyral has a hydroxyl group content of from 18 to 23% by weight. The polyvinyl butyral composition according to any one of claims 3 to 6 is for use in the preparation of a bonded glass. The polyvinyl butyral composition according to any one of claims 3 to 6 is for use in the preparation of a bonded glass for use in the automotive industry, the construction field, and the solar cell field.