TWI538942B - Transparent resin composition having excellent medicament resistant and durability, being stable under natural environmental conditions and more severe nattural environmental conditions, or for use under the same or more severe condition - Google Patents

Description

A transparent resin composition which is stable under the natural environmental conditions and under the harsh natural environmental conditions or under the stricter use conditions, and which is excellent in chemical resistance and durability, and a product using the same

The present invention relates to a novel polycyclohexylene dimethylene terephthalate (PCTFE) copolyester composition which is stable under natural environmental conditions or under the same or more severe use conditions. Invention of a product using the composition.

The helmet of one of the safety equipment is actively assembled and used in many fields including the industrial field, the circulation field, the construction and civil engineering fields, and the products used in social life. Polycarbonate (PC), acrylic acid-butadiene-styrene resin (ABC) or glass fiber reinforced thermosetting resin (FRP) of the material is widely known (Patent Document 1 Japanese Patent Laid-Open Publication No. 2003-105620) ). These polycarbonates have the following characteristics and are widely used in other technical fields.

Polycarbonate is a transparent amorphous resin. This resin has a small mold shrinkage ratio, good dimensional accuracy, and small water absorption, so that the dimensionality is good. It has excellent impact resistance and creep, and is considered to be a good material in terms of heat resistance, electrical properties, automatic fire extinguishing, and light resistance.

The problem with this material is that it is indicated that there is no resistance (Non-Patent Document 1 "Plastic Data Sheet", Asahi Kasei Amidas Co., Ltd. and "Plastic" Editorial Department, edited, December 1, 1999, Industrial Co., Ltd. 599 pages and 605 pages).

The helmet used outside the house is in daylight and high temperature, or although it is low temperature However, when used under severe conditions such as wet conditions, the material of the polycarbonate constituting the helmet is highly polluted, and in this case, the treatment of removing the surface contamination by the drug treatment is indispensable. If such a treatment is carried out, the polycarbonate may suddenly be dissolved or swollen, whitened or broken, broken, and is considered to be problematic as a product.

Table 1 shows the results of the resistance of polycarbonate to various drugs measured by the investigator and the like.

The table shows the assessment divided into 10 levels. The larger the value, the greater the resistance. It is known that it is easily attacked by alkali or an organic solvent, and there is no stability to these drugs. Further, since there is an ester bond, when exposed to an alkaline solution or high-temperature water, the polycarbonate causes hydrolysis, and the decomposition of the product using the material can be considered. On the other hand, when water or an acid is present individually, it is considered that there is almost no progress of hydrolysis under normal temperature or low temperature conditions. In the high-temperature and high-humidity environment, due to the presence of high-temperature water, there is a concern that a hydrolysis reaction may occur.

When an alkaline solution is present, hydrolysis may be accelerated by the influence of its concentration and temperature. When used as a material of a product, it is necessary to use these effects in consideration of these effects.

In the polycarbonate helmet having the above problems, the following measures have been taken for the resin, but it has been pointed out that there is a sudden breakage in use, and it is considered that the uneasiness cannot be eliminated.

There is known a polycarbonate resin molded body (Patent Document 2, JP-A-2007-210138), which is composed of a laminate, and the laminate system is based on a polycarbonate resin and is on the substrate. The non-absorbent barrier layer having the ultraviolet curable resin coating film as the first layer is formed on at least one surface, and the water absorbing ultraviolet curable resin coating film as the second layer is formed on the first layer. The fog layer.

It is known that a plastic goggle lens such as polycarbonate or a helmet face shield is provided with physical properties such as high adhesion and high abrasion resistance, and the film formed can be anti-fog due to hydrophilicity on the inner surface. The surface of the water-repellent waterproofing film is water-repellent and the oil-repellent film is anti-fouling (Patent Document 3, JP-A-2006-089859).

A multilayer article is known which consists of a substrate layer and an uppermost layer of one or more layers; the substrate layer comprising: from about 15% by weight to about 75% by weight based on the total weight of the fiber-reinforced polymer substrate And one or more kinds of thermoplastic polymers; the uppermost layer includes one or more thermoplastic polymers containing one or more kinds of 1,3-dihydroxybenzene and one or more structural units derived from an organic dicarboxylic acid; (Patent Document 4, JP-A-2008-500204).

There is known a resin molded article in which a Scratch Resistance organic hard coat layer having a haze value of 5% or less is provided on one surface of a substrate, and the following coated material is provided on the other side of the substrate. The formed anti-fogging organic hard coat layer (Patent Document 5, Japanese Laid-Open Patent Publication No. 96/041831).

a composition characterized by comprising the following polymer mixture (polymer blend), wherein the polymer mixture is non-releasable: the polymer mixture is characterized in that: (a) a group containing a free amine group and a free anhydride group, and a combination of the combinations a component further comprising a prepolymer of a dianhydride and a diamine-derived building unit, and (b) a polymer comprising a structural group and a terminal group and a reactive component selected from the group consisting of the combination The reactive component is derived from the above-mentioned free anhydride group and free amine group, or a combination thereof (Patent Document 6: JP-A-2010-51037).

There have also been attempts to use polycarbonate alloys as raw materials. Polycarbonate and acrylic butadiene styrene resins and polycarbonates and polyesters are mostly opaque, and transparency is not available in the necessary technical fields. The inventors of the present invention have also reviewed the results of their use, and have not been sufficiently resistant to chemicals, and have found that it is difficult to use them as raw materials such as helmets.

The inventors of the present invention have been working hard on the development of safety appliances such as helmets. Specifically, in addition to the shape of the helmet, it is necessary to review the materials used for the aforementioned problem. It is considered that it is inherently difficult to use polycarbonate resin in the future. However, in order to develop a novel resin as a material for a helmet, such as the development of a viewing resin, and a considerable degree of development, it is indeed a difficult situation. As a result, it has been found that a material suitable for use in a stable state under the use conditions can be developed by using a conventional resin, and a practical solution can be solved.

As will be described later, the known polycyclohexylene dimethylene terephthalate copolyester resin differs from the conventional polycarbonate in general conditions. The use is considered to be resistant. However, the inventors of the present invention have to use the field of poly(terephthalic acid) cyclohexylidene methylene ester copolyester, which is not a good environment in indoor facilities, but in a natural environment condition that has not been used in the past or Materials with stable weatherability and resistance under equivalent or harsher conditions of use. Also, to be able to tolerate such conditions, consider adding other substances to change their characteristics. In consideration of the premise of suppressing the decomposition of poly(p-phenylene terephthalate), it is necessary to delineate substances that have a dominant property in suppressing decomposition, and based on the results, countermeasures against which the dominant factor cannot be concealed are required. . In any case, it is considered effective to upgrade it so that it can tolerate the environment when it is used. From this point of view, the poly(ethylene terephthalate) cyclohexyl dimethylene methyl ester copolyester resin was reviewed.

Poly(terephthalic acid) cyclohexyl dimethylene copolyester resin is known in the art (Patent Document 7 U.S. Patent No. 2,901,466). After that, the poly(trimethylene terephthalate) copolyester resin of the polyethylene terephthalate of Eastman Chemicals Co., Ltd. is also known (for example, JP-A-H11-512484, JP-A No. 3432830, and the like). Further, as for the production method, the specification of the U.S. Patent No. 5,106,944 (Patent Document 9) and the specification of U.S. Patent No. 5,668,243 (Patent Document 10) are known. After the improvement, the copolyester of poly(trimethylene terephthalate) cyclohexyl dimethylene ester was confirmed to have impact resistance, small creep, heat resistance, and electrical properties. In the formation of the copolyester, the reaction of the diol component with the dicarboxylic acid component can be carried out using conventional polyester polymerization conditions. The copolyester is produced by a transesterification reaction. When the copolyester is produced from an ester type dicarboxylic acid component, the reaction process can be carried out by 2 The steps are made. In the first step, the diol component and the dicarboxylic acid component such as dimethyl isophthalate and dimethyl terephthalate are at a high temperature, generally about 180 ° C to about 280 ° C and about 0.0. The reaction is carried out at a pressure of about 60 psig. Desirably, the temperature of the transesterification reaction is from about 190 ° C to about 240 ° C, and the desired pressure is from about 15 to about 40 psig. The reaction product is heated under reduced pressure at a higher temperature to form a polyester by detachment of the diol. The diol is easily volatilized under these conditions and is removed from the reaction system. The polycondensation step of the second step is at a higher vacuum, typically from about 240 ° C to about 300 ° C, desirably from about 245 ° C to about 290 ° C, and most desirably from about 250 ° C to about 270 ° C. The polyester is continued until the desired degree of polymerization is determined by IV. The polycondensation step is carried out under reduced pressure in the range of about 400 to about 0.1 mmHg (torr) (Patent Document 11 Japanese Patent Publication No. 2003-506592, and Japanese Patent Publication No. 2002-523647). . In addition, it is also known that a polyester or a oligomer thereof is supplied to a vertical agitation type film evaporator in a molten state, and a polyester having a higher polymerization degree than that before being supplied is known (Patent Document 13 Japan) JP-A-2000-309631).

As a result of active research, polyterephthalic acid is known. Isophthalic acid 1,4-cyclohexylene dimethylene methyl ester, and polyesters such as these copolyesters are hydrolyzed by a small amount of water, and work is done to avoid hydrolysis (Patent Document 14 Japanese Patent Laid-Open No. 2007-285944) Bulletin).

There is also known a polyester support for an antifogging film which is a biaxially stretched polyester film characterized by comprising a polyester having a metal sulfonic acid group and a polyalkylene glycol as a copolymer component. Polybutylene terephthalate An ultraviolet absorber is added to the polyester support for an anti-fog film formed by the methylene ester (Patent Document 15: JP-A-2004-359707).

Further, it is also known to add carbodiimide or the like to prevent hydrolysis of the polyester (Patent Document No. 11-506847).

It is also known to use a film having an ultraviolet shielding effect in pattern transfer (Patent Document 17 Japanese Patent No. 4105919). Further, a thermoplastic polyester molding composition characterized by containing a polyester resin and an ultraviolet stabilizer, and which is suitable for preparing a molded article resistant to decomposition and discoloration when exposed to ultraviolet rays for a long period of time (Patent Document 18 Japanese Special) Table No. 11-323100).

A polymer composition for improving wear characteristics, comprising polystyrene, polycarbonate, polyetherimide, polyolefin, polyfluorene, polyether oxime, polyacetal, nylon, polyester, polyphenylene sulfide, a mixture of at least two different polymers selected from the group consisting of polyphenylene ether and polyetheretherketone, and at least one elastomer for strengthening the polymers, the elastomer exhibiting a performance of less than 50,000 pig The tensile modulus (Patent Document 19, Patent No. 3,647,036) is a crack-resistant property having higher abrasion resistance, a lower yield strength, and a large transfer film ductility.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-105620

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-210138

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-089859

[Patent Document 4] Japanese Patent Publication No. 2008-500204

[Patent Document 5] Japanese Re-issue 96/041831

[Patent Document 6] Japanese Patent Publication No. 2010-51037

[Patent Document 7] US Patent No. 2,901,466

[Patent Document 8] Japanese Patent Publication No. Hei 11-512484, Japanese Patent No. 3432830

[Patent Document 9] U.S. Patent No. 5,106,944

[Patent Document 10] US Patent No. 5,668,243

[Patent Document 11] Japanese Patent Publication No. 2003-506592

[Patent Document 12] Japanese Patent Publication No. 2002-523647

[Patent Document 13] Japanese Patent Laid-Open Publication No. 2000-309631

[Patent Document 14] Japanese Laid-Open Patent Publication No. 2007-285944

[Patent Document 15] Japanese Patent Laid-Open Publication No. 2004-359707

[Patent Document 16] Japanese Patent Publication No. 11-506847

[Patent Document 17] Japanese Patent No. 4105919

[Patent Document 18] Japanese Patent Publication No. 11-323100

[Patent Document 19] Japanese Patent No. 3647036

[Non-patent literature]

[Non-Patent Document 1] "Plastic Data Book" was edited by Asahi Kasei Amidas Co., Ltd. and "Plastic" Editorial Department. On December 1, 1999, the Industrial Survey of the Co., Ltd. issued 599 pages and 605 pages.

The present inventors have worked hard to develop and produce a helmet or the like as described above. When using a polycarbonate resin used as a conventional material, it lacks resistance, that is, Become a problem and work hard toward it. It is expected that it is difficult to process the resistance of the polycarbonate resin used in the past, and it is difficult to develop a novel resin of the material of the helmet.

Therefore, it is considered that it is a matter of urgency to use existing resin processing to become a material suitable for use.

The first object to be solved by the present invention is to provide a novel transparent resin composition which has sunlight, rain water or washing water, air pollutants, air in a product such as a helmet or the like under use conditions. The presence of oxygen is stable under natural environmental conditions in a high temperature, high humidity or low humidity environment exposed to sunlight and under the harsher natural environmental conditions or under the same or more severe conditions. And have resistance.

A second problem to be solved by the present invention is to provide a helmet, a helmet for a helmet, a lens for goggles or glasses, an outer box for housing storage, and a sheet for exterior distribution, and materials used for helmets and the like. Under the conditions of use, there are sunlight, rain or washing water, atmospheric pollutants, the presence of oxygen in the air, or the natural environment under the environment of high temperature, high humidity or low humidity illuminated by sunlight or the same or It is stable under more severe conditions of use and has weather resistance and chemical resistance.

(1) It is known that Tritan (hereinafter, manufactured by Eastman Chemical Co., Ltd.) of a poly(ethylene terephthalate) cyclohexyl dimethylene copolyester resin has no resistance to the conventional polycarbonate resin, and is generally The condition is fully durable. At the same time, it was found that the characteristics other than drug resistance were All the properties of the polycarbonate resin have the same impact resistance, small creep, heat resistance, electrical properties, automatic fire extinguishing property and light resistance, and are also usable in the past.

(2) Tritan, a polybutylene terephthalate dimethylene methyl ester copolyester resin, for the use of this material as a material for the presence of sunlight in sunlight, rain or washing water, atmospheric pollutants, and oxygen in the air Under the natural environment conditions of high temperature, high humidity or low humidity which are irradiated with sunlight, or under the stricter conditions of use, the expected results cannot be obtained. Knowing that it is to be a material that can withstand this condition requires specific treatment.

(3) For the products of Tritan, helmets, etc. of poly(terephthalic acid) cyclohexyl dimethylene methyl ester copolyester resin in the presence of sunlight, rain or washing water, atmospheric pollutants, and oxygen in the air, In the environment of high temperature, high humidity or low humidity, which is exposed to sunlight, under natural environmental conditions or operating conditions, it is necessary to find out which material to coexist in order to be stable. It is known that Tritan of a poly(ethylene terephthalate) cyclohexylene dimethylene methyl ester copolyester resin is more stable than a conventionally existing resin, and various stabilizers generally known may not necessarily be effective for this substance. At this time, it is necessary to make it possible to withstand a specific condition and a specific material having a certain effect, and it is known that it is necessary to clarify which one of the materials is effective. Then, in the presence of light, the presence of water, the presence of trace amounts of chemical substances, etc. (causes of instability, etc.) or the cause of substances (substances that are unstable, etc.), it is necessary to consider countermeasures. For the main reason, in order to deal with this cause, what kind of substance should be used, it is necessary to decide.

(4) First, it is necessary to clarify whether or not the weathering agent acts as a countermeasure against the prevention of photodegradation, thermal deterioration, and hydrolysis, and in particular, it is determined which substance acts effectively.

a. Using a photodegradation inhibitor as a weathering agent

The photo-deterioration preventing agent is a case where light is grasped by an ultraviolet ray preventing agent and a case where infrared rays are to be considered. A compound that prevents oxidation degradation due to light (mainly ultraviolet light) is generally referred to as a light stabilizer. It can be a UV absorber with a chain-inhibiting effect, a hindered amine-based stabilizer with a radical scavenging action, and a benzoic acid stabilizer which has both functions. Ultraviolet absorbers are those that absorb ultraviolet light and are harmless to plastics. Mainly benzotriazole and diphenyl ketone are used. The hindered amine-based stabilizer is an effect of capturing a radical generated by ultraviolet rays and preventing coloration and gloss retention. It is also effective for preventing thermal oxidation. As the ultraviolet preventive agent, various preventive agents are known. But not all have an effect, and it is considered that only those with special functions are limited. For example, UVa (Novapex U-110 manufactured by Mitsubishi Chemical Corporation), UVb (manufactured by Irganox BASF Co., Ltd.), UVc (manufactured by Seesorb 706), color difference, transmittance, Charpy Impact strenggth, The point of tensile breaking strength could not give satisfactory results, and finally it was judged to be ineffective.

UV-3638 (manufactured by Sun Chemical Co., Ltd.), an ultraviolet absorbing agent of an oxazinone-based compound, has no decrease in transmittance and does not have a change in the impact strength of the sand sputum, and it is judged that it can be effectively used as a photodegradation prevention. Although there is no problem at the point of impact strength of the sand shovel, it is concluded that it cannot be used alone. The use as a photodegradation preventing agent cannot be a major factor.

b. Utilization of hydrolysis inhibitors as weathering agents

If a stable substance such as Tritan is likely to cause a hydrolysis reaction under the conditions of use, it cannot be known from the conventional idea. On the other hand, in the poly(trimethylene terephthalate) cyclohexyl dimethylene methyl ester copolyester having an ester bond, the use in the presence of water is a property of hydrolysis depending on environmental conditions, so that it is necessary to pay attention to it. The conclusion of the countermeasure against hydrolysis. For example, only water or acid is hardly hydrolyzed at normal temperature or low temperature, but in a high-temperature and high-humidity environment, only water is hydrolyzed, and in the presence of a solution containing an alkali component, the concentration is Under the influence of temperature, it is considered to accelerate hydrolysis.

(a) Add 5% of E-pellet diluted with PET to carbodilite of Nisshinbo Chemical Co., Ltd. in Tritan TX1001.

When E-pellet is added to TX 1001, in the initial state, TX1001 and PET cannot be uniformly mixed, resulting in turbidity and insufficient permeability (transmittance 80 up and down), and slight yellowing is also observed, so chromatic aberration and transmittance cannot be considered as Fully satisfactory results. However, the chromatic aberration after the weather resistance test for 300 hours was promoted, and the transmittance was hardly lowered and the stability was passed. The conclusion is that effective results can be obtained for weatherability.

(b) Next, carbodilite of Nisshinbo Chemical Co., Ltd. was added to Tritan TX1001 to form LA-10.5% in powder form.

When LA-1 was added to TX 1001, the decrease in transmittance due to turbidity due to the addition of E pellets was not observed, and the transmittance at the time of adding LA-1 to TX1001 was about 88% of the transmittance of TX1001. It is 90% and can get satisfactory results.

There was almost no decrease in the transmittance due to the promotion of the weather resistance test for 300 hours, and satisfactory results were also obtained for the weather resistance.

This is because when the hydrolysis is caused, the ester bond is cut to absorb light, and the transmittance is lowered, so that hydrolysis is not caused. In the sand impact test, the initial physical properties were NB (non-break), but there was a significant decrease at 100 hours, and satisfactory results could not be obtained. This is considered to be because the ultraviolet rays cause the molecular chain to be cut.

The effect on Tritan is that there is no problem at the point of transmittance, but there is a problem that the impact strength of the sand is low, and the solution to the hydrolysis inhibitor is not sufficient.

c. Using a heat inhibitor as a weathering agent

Since heating imparts activation to a substance, it is considered that the heating operation is sufficiently effective. However, there are many cases in which the prevention of heating contributes to the stabilization of the substance. It has been found that what can be obtained by using a photodegradation preventing agent and a hydrolysis inhibitor for a substance having a stability of Tritan or the like as a cause of heating prevention.

Next, the results of the combination of the photodegradation measures (addition of carbodilite LA-1) and the countermeasures of photodegradation and hydrolysis were compared as follows.

In the countermeasure against photodegradation, the initial physical properties of the sand impact strength and the transmittance were high, and the weather resistance test was hardly observed to decrease for 300 hours.

In the hydrolysis countermeasure, the initial physical properties of the sand impact strength and the transmittance were high, and the transmittance for the weather resistance test for 300 hours was hardly observed. The impact strength of the sand raft is greatly reduced.

On the other hand, the combination of the photodegradation countermeasure and the hydrolysis countermeasure was that the impact strength of the sand blast impact strength and the transmittance was high, and the weather resistance test was hardly observed for 300 hours. Further, as for the tensile properties, improvement was also observed, and the weather resistance test was promoted for almost 300 hours, and no decrease was observed, and satisfactory results were obtained.

In addition, it is said that the photo-deterioration countermeasure and the hydrolysis countermeasure are simply used in combination, and the effect of the high weather resistance (heating inhibitor) can be obtained by the double-effect of the photo-deterioration countermeasure and the hydrolysis countermeasure.

(5) According to the above results, the invention as described below can be obtained.

a transparent resin composition which is stable and weather resistant and resistant under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use, is in a pair The cyclohexylene dimethylene methyl ester copolyester contains a UV absorber composed of a benzoxazinone compound.

b. A transparent resin composition which is stable and has weather resistance and chemical resistance under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use, is in a pair The cyclohexylene dimethylene methyl ester copolyester contains a hydrolysis inhibitor composed of carbodiimide.

c. A transparent resin composition which is stable and has weather resistance and chemical resistance under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use, is in a pair The cyclohexylene dimethylene methyl ester copolyester contains a UV absorber composed of a benzoxazinone compound and a hydrolysis inhibitor composed of carbodiimide.

d, as described in any of the above a to c under natural environmental conditions and A transparent resin composition which is stable and has weather resistance and chemical resistance under severe natural environmental conditions or a more severe use condition, and contains an antioxidant and a heat resistant material.

e. A safety helmet that is stabilized under natural environmental conditions and under the harsh natural environmental conditions or under the stricter or more severe use conditions as described in any of the above a to d. Manufacturer of transparent resin composition having weather resistance and chemical resistance.

f. A mask for a safety helmet, which is used under natural environmental conditions and under the harsh natural environment conditions or under the stricter conditions of use as described in any of the above a to d Manufacturer of a transparent resin composition that is stable and has weather resistance and chemical resistance.

g. A lens for spectacles, which is stabilized under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use as described in any of the above a to d. It is a manufacturer of a transparent resin composition having weather resistance and chemical resistance.

h. An outer casing for storing articles, which uses the conditions as described in any of the above a to d under natural environmental conditions and under the harsh natural environmental conditions or the same or more severe conditions. Produced by a transparent resin composition which is stable and has weather resistance and chemical resistance.

i. A sheet for exterior distribution, which is used under natural environmental conditions and under the harsh natural environment conditions or under the stricter conditions of use as described in any of the above a to d Manufacturer of a transparent resin composition that is stable and has weather resistance and chemical resistance.

j. A frame for glasses and a handle for glasses, which are used as in the above a to d A transparent resin composition having weather resistance and chemical resistance which is stable under natural environmental conditions and under such harsh natural environmental conditions or under the stricter use conditions.

Further, the inventors of the present invention have found that a transparent resin composition which is stable and has weather resistance and chemical resistance under the above-mentioned natural environmental conditions or under the stricter use conditions can be used in a small gear having lubricating properties. Used as a gear material.

According to the present invention, it is possible to provide a transparent resin composition which is stable in weather and resistance under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use. Characterized in that the poly(trimethylene terephthalate) cyclohexyl dimethylene methyl ester copolyester comprises a UV absorber formed from a benzoxazinone compound, and a hydrolysis inhibitor formed from carbodiimide. Or a UV absorber composed of a benzoxazinone compound and a hydrolysis inhibitor composed of carbodiimide, and a transparent resin which is stable under weathering conditions and has weather resistance and chemical resistance. In contrast, a transparent resin composition which is stable and has weather resistance and chemical resistance under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use or the like is provided. It is characterized by further containing an antioxidant and a heat resistant material. These transparent resin compositions can be used as a helmet, a mask for a helmet, a lens for glasses, an outer case for storing articles, a plate for exterior arrangement, a frame for glasses, and a glasses temple.

[Best Mode for Carrying Out the Invention]

The poly(trimethylene terephthalate) cyclodextylene dimethylene methyl ester copolyester used in the present invention is described in the following publication (Japanese Patent No. 3432830, Japanese Patent Application Laid-Open No. Hei 11-506847).

In the formation of the copolyester, the reaction of the diol component with the dicarboxylic acid component can be carried out using conventional polyester polymerization conditions. The copolyester is produced by a transesterification reaction. When a copolyester is produced from an ester type dicarboxylic acid component, the reaction process can be constituted by two steps. In the first step, the diol component and the dicarboxylic acid component such as dimethyl isophthalate and dimethyl terephthalate are usually at a temperature of about 180 ° C to about 280 ° C and about 0.0 to a high temperature. The reaction was carried out at a pressure of about 60 psig. Desirably, the temperature of the transesterification reaction is from about 190 ° C to about 240 ° C, and the desired pressure is from about 15 to about 40 psig. The reaction product was heated under reduced pressure at a high temperature to form a polyester by detachment of the diol. The diol is easily volatilized under these conditions and is removed from the reaction system. The polycondensation step of the second step is carried out at a higher vacuum, typically from about 240 ° C to about 300 ° C, desirably from about 245 ° C to about 290 ° C, and most desirably from about 250 ° C to about 270 ° C. To a polyester having a desired degree of polymerization determined by IV. The polycondensation step is carried out under reduced pressure in the range of about 400 to about 0.1 mmHg (Japanese Patent Publication No. 2003-506592).

The molded article of the present invention is produced from a copolyester comprising an acid component and a diol component and having an inherent viscosity of 0.4 to 1.1 dl/g, and the acid component comprises: derived from terephthalic acid 90 to 40 mol% (ideally 85 to 52 mol%, more desirably 83 to 52 mol%) and 10 to 60 mol% of cyclohexanedicarboxylic acid as an additional dibasic acid (ideal Is a repeating unit of 15 to 48 mol%, more desirably 17 to 48 mol%, and the diol component comprises: derived from 1,4-cyclohexanedimethanol (ideally 80 to 100 mol%, More preferably, it is a repeating unit of 85 to 100 mol%, more preferably 90 to 100 mol%, and still more preferably 95 to 100 mol%.

Tritan, which is obtained using East Polyethylene's poly(trimethylene terephthalate) cyclodecyl dimethylene copolyester, is known to have the following grades.

TX1000: Heat resistant to 99 ° C (HDT 0.455 MPa).

TX1001: The stage for injection molding of the TX1000.

TX1500HF: The high flow level of the TX1000.

TX2000: Heat resistant 109 ° C (HDT 0.455 MPa) grade.

TX2001: The stage for injection molding of the TX2000.

The physical properties of the polytrimethylene terephthalate dimethylene methyl ester copolyester resin of the present inventors and the Tritan (trade name) were examined for resistance. The results are shown in Table 2 below.

The contents shown in A to X of Table 2 are as follows.

From the above, it was confirmed that the poly(ethylene terephthalate) cyclohexylene dimethylene methyl ester copolyester resin has good physical properties and resistance.

The characteristics of Tritan are as follows.

High transparency. Light transmission rate is 92% (TX2000).

The impact resistance is the same as that of polycarbonate. High impact resistance 15ft-Ib/in.

Flexural elastic modulus. 240kpsi.

High heat resistance (120 ° C) (glass transition temperature).

The specific gravity is 1.17, which is lower than polycarbonate and PET.

Good environmental properties (wherein, there is no plasticizer such as bisphenol A.).

Also, as shown in the table below.

As described above, Tritan (trade name) of a poly(trimethylene terephthalate) cyclohexyl dimethylene copolyester resin is a highly stable substance under normal conditions.

It can be seen that Tritan of poly(terephthalic acid) cyclohexyl dimethylene copolyester resin is under natural environmental conditions or the same or more severe conditions of use, in particular, products of helmets and the like are in use conditions. Sunlight, rainwater or washing water, atmospheric pollutants, the presence of oxygen in the air, or the natural environment under high temperature, high humidity or low humidity, which is irradiated by sunlight, is more or less severe. The existence cannot be stabilized under the conditions of use. If it is used in general, it is necessary to mix a specific substance so that it can be stably present or the like.

The present invention is as follows.

a transparent resin composition which is stable and weather resistant and resistant under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use, is in a pair The cyclohexylene dimethylene methyl ester copolyester contains a UV absorber composed of a benzoxazinone compound.

b. A transparent resin composition which is stable and has weather resistance and chemical resistance under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use, is in a pair The cyclohexylene dimethylene methyl ester copolyester contains a hydrolysis inhibitor composed of carbodiimide.

c. A transparent resin composition which is stable in weather conditions and resistant under natural environmental conditions or under the stricter conditions of use, and is in the form of polyethylene terephthalate dicyclohexylene dimethylene Ester copolyester contained in benzene An ultraviolet absorber composed of an oxazinone compound and a hydrolysis inhibitor composed of carbodiimide.

d. as described in any of the above a to c, which is stable under the natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use, and has weather resistance and chemical resistance. A transparent resin composition comprising an antioxidant and a heat resistant material.

Using this property, materials which are the following products can be used.

e. A safety helmet which is transparent and has weather resistance and chemical resistance under natural environmental conditions or under the same or more severe use conditions as described in any one of the above a to d. Manufacturer of resin composition.

f. A mask for a safety helmet, which is used under natural environmental conditions and under the harsh natural environment conditions or under the stricter conditions of use as described in any of the above a to d Manufacturer of a transparent resin composition that is stable and has weather resistance and chemical resistance.

g. A lens for spectacles, which is stabilized under natural environmental conditions and under the harsh natural environmental conditions or under the stricter conditions of use as described in any of the above a to d. It is a manufacturer of a transparent resin composition having weather resistance and chemical resistance.

h. An outer casing for storing articles, which uses the conditions as described in any of the above a to d under natural environmental conditions and under the harsh natural environmental conditions or the same or more severe conditions. Produced by a transparent resin composition which is stable and has weather resistance and chemical resistance.

i. A board for exterior distribution, which uses the same or more severe use under natural environmental conditions as described in any of the above a to d. Produced by a transparent resin composition which is stable and has weather resistance and chemical resistance under conditions.

j. A spectacles frame and a spectacles for spectacles, which are weatherable and stable under natural environmental conditions or use conditions as described in any one of the above a to d, and have weather resistance and chemical resistance. Manufacturer of transparent resin composition.

Further, the inventors of the present invention have found that a transparent resin composition which is stable and has weather resistance and chemical resistance under the above-mentioned natural environmental conditions or under the stricter use conditions can be used in a small gear having lubricating properties. Used as a gear material.

The process of determining the hydrolysis reaction inhibitor formed by the ultraviolet absorber and the carbodiimide formed by the benzoxazinone-based compound is not simply determined, and various candidates are selected by the experience of the present inventors, and then experimentally. decided. The contents are explained below.

(1) In order to solve the problem by using an existing resin, a known resin was searched, and a resin having resistance was examined, and Tritan of a poly(trimethylene terephthalate) cyclomethylene dimethylene ester copolyester resin was found to have resistance. In addition, it has been found that resistance to properties other than chemical resistance, such as the properties of conventional polycarbonate resins, impact resistance, small creep, heat resistance, electrical properties, automatic fire extinguishing properties, and light resistance are also The same level of features that can be used.

(2) The inventors of the present invention, such as Tritan, which is a polybutylene terephthalate dimethylene methyl ester copolyester resin, is used under the conditions of use of products such as helmets, rain water or washing water, air pollutants, And the presence of oxygen in the air, followed by the natural ring of high temperature, high humidity or low humidity Materials that are stable and resistant under the conditions of the environment or under the stricter conditions of use, whether or not there is weather resistance, are tested by a weathering test machine, and the expected results are not obtained. That is, it can be seen that there is a need for special efforts.

(3) Secondly, the tritan of poly(terephthalic acid) cyclohexyl dimethylene methyl ester copolyester resin, sunlight, rain or washing water, atmospheric pollutants, and air in the use conditions of products such as helmets In the presence of oxygen, the surface treatment or the formation of a laminate can be reviewed as a countermeasure against the stability of natural environment conditions under high temperature, high humidity, or low humidity, or operating conditions. It seems that we can't expect exceptionally good results, so we repeat the experiments below.

The countermeasure against deterioration of photodegradation, thermal deterioration, and hydrolysis is examined for measures that are particularly problematic.

The weathering test is the result of experiments from various angles, and results can be obtained with different results from the original attempt.

About drug sex

(a) Tritan obtained from polybutylene terephthalate dimethylene methyl ester copolyester resin with resistance, small creep, heat resistance, electrical properties, automatic fire extinguishing and light resistance resin, review Countermeasures for photodegradation, thermal degradation, and hydrolysis reaction.

(a) photodegradation

As a countermeasure against photodegradation, we are looking for a UV absorber for PET, and NOVAPEX U-110 (manufactured by Mitsubishi Chemical Corporation), Seesorb 703 (made by Shiraishi Calcium Co., Ltd.), Seesorb 706 (White Stone Calcium Co., Ltd.) (Imganox 1010 (manufactured by BASF Corporation), Tritan was added to a polybutylene terephthalate dimethylene methyl ester copolyester resin to confirm the effect. This is not to be selected as long as it is a UV absorber, but it is determined whether it is necessary to preliminarily select an ultraviolet absorber which is considered to be appropriate, and then determine whether it is appropriate or not, and the result is determined in consideration of a combination with other additives. The decision can be made by the result of (i) below.

(i) UV absorber (UVa: Novapex U-110 1%, UBb: Seesorb 703 0.25% + Irganox 1010 0.25%) was added to the TX2001 of the injection molding grade of TX2000 which is heat-resistant at 109 ° C (HDT 0.455 MPa) in Tritan. .

The initial physical properties of Izod impact strength were good when UVa was added to TX2001 (551.3). The result of adding UVb to TX2001 gave a result of half the degree of addition of UVa (232.2), and a sufficiently satisfactory result could not be obtained.

The initial physical properties of the AOC strength were excellent, and the UVa addition of TX2001 was promoted to promote the weather resistance test. Significant yellowing was observed by visual observation at 100 hours (color difference measurement was about 20), and a sufficiently satisfactory result could not be obtained.

Further, the amount of UVa added to TX2001 was increased to 2%, and the color difference measurement value was not improved, and a sufficiently satisfactory result could not be obtained.

(ii) Next, a UV absorber (UVa: Novapex U-110 1%, UVc: Seesorb 706 + Irganox 1010 0.25%) was added to TX1001 of the injection molding grade of TX1000 of Tritan's heat-resistant 99 ° C (HDT 0.455 MPa) grade.

Even if Uva is added to TX1001, the color difference measurement value does not improve, no Can get fully satisfactory results.

Even if Uvc is added to TX1001, the color difference measurement value is not improved, and a sufficiently satisfactory result cannot be obtained.

The conclusion can be obtained by the following.

(iii) At the beginning, it was considered that UV 3638 (manufactured by Sun Chemical Co., Ltd.), which can be searched again, could be used. Add UV 3638 0.5% to Tritan TX1001. The initial physical properties are that the sand impact strength is NB (no breakage), and the transmittance is also high at the initial physical properties of about 90. After the weather resistance test was promoted, the impact strength and the transmittance of the sand were hardly observed after 300 hours, and satisfactory results were obtained.

It is considered that (in practical use) is questionable.

It is not a helmet that is often placed in an outdoor environment. It is considered (practical) to be no problem if there is no problem for 200 to 300 hours.

(b) Countermeasures against hydrolysis reaction

The necessity of inhibiting the hydrolysis reaction: for the ester-bonded poly(trimethylene terephthalate) cyclohexyl dimethylene ester copolyester, it is stable under natural environmental conditions or under the stricter conditions of use. The material that is resistant is that it is considered necessary to consider the environment in which water exists. Depending on the conditions of use, it is necessary to prevent the hydrolysis reaction by the nature of the hydrolysis reaction. For example, only water or acid will hardly hydrolyze at normal or low temperatures. In the high-temperature and high-humidity environment, only water will be hydrolyzed, and in the presence of an alkali component, the hydrolysis will be accelerated by the concentration and temperature.

(i) 5% by weight of E pellets diluted with PET in carbodilite of Nisshinbo Chemical Co., Ltd. was added to Tritan TX1001.

When E pellets were added to TX1001, TX1001 and PET did not mix uniformly in the initial state, and turbidity occurred. The permeability was poor (transmittance of about 80), and there was a slight yellowing. The chromatic aberration and transmittance could not be satisfactorily obtained, but almost no one was observed. The color difference after 300 hours of the weather resistance test was promoted, and the transmittance was lowered, and the weather resistance was obtained as a result.

(ii) Next, carbodilite of Nisshinbo Chemical Co., Ltd. was added to Tritan TX1001 to prepare a powdery LA-1 0.5% by weight.

When LA-1 was added to TX1001, the decrease in transmittance due to turbidity at the time of E-pill addition was not observed, and the transmittance with respect to TX1001 was about 88%, and the transmittance when adding LA-1 to TX1001 was 90%. Satisfied results.

When the weather resistance test was promoted for 300 hours, the transmittance was hardly observed, and satisfactory results were obtained for the weather resistance.

This is because when the hydrolysis is caused, the ester bond is cut to absorb light, and the transmittance is lowered, so that hydrolysis is not caused.

The initial physical properties of the sand blast impact test were NB (no breakage), but it was greatly reduced at 100 hours, and satisfactory results could not be obtained. This is considered to be because the molecular chain is cut by ultraviolet rays.

In terms of the specifications of the glasses, the transmittance of the lens is specified to be 85% or more.

(c) The above is to make the poly(trimethylene terephthalate) cyclohexyl dimethylene methyl ester copolyester In the countermeasure against photo-deterioration and the countermeasure against the hydrolysis reaction under the natural environment conditions or under the conditions of use, the inventors of the present invention have clarified the countermeasures against photodegradation and The countermeasure against the generation of the hydrolysis reaction is effective. However, in order to stabilize and be resistant under natural environmental conditions or under the stricter conditions of use, there are concerns about the need for temperature, countermeasures against high-temperature water, and oxygen present in the air. The countermeasures, such as countermeasures against the pollutants present in the air. In order to eliminate this uneasiness, when countermeasures against photodegradation and prevention of hydrolytic decomposition are simultaneously applied, it can be said that it is stable and resistant under natural environmental conditions or under the same or more severe use conditions. Medicinal materials.

Then, a test for the combination of photodegradation measures (addition of UV3638 by Sun Chemical Co., Ltd.) and hydrolysis reaction suppression measures (addition of carbodilite LA-1) was carried out.

(i) UV3638 0.5% and LA-1 0.25% were added to Tritan TX1001, UV3638 0.5% and LA-1 0.25% were added to TX2001, and UV 3638 0.25% and LA-1 0.25% were added to TX2001.

When UV3638 and LA-1 were added to TX1001, the initial physical permeability was about 87%, and the sand blast impact was also NB (no breakage), and satisfactory results were obtained.

Further, after the weather resistance test was promoted for 300 hours, the transmittance and the impact strength of the sand smash were hardly observed, and satisfactory results were obtained.

When UV3638 and LA-1 were added in TX 2001, the initial physical transmittance was about 87%, and the sand impact strength was also 70.9, which gave satisfactory results. Further, after the weather resistance test was promoted for 300 hours, the transmittance and the impact strength of the sand smash were hardly observed, and satisfactory results were obtained.

When a half amount of UV3638 and a half amount of LA-1 were added in TX2001, the initial physical permeability was about 88%, and the sand impact strength was also 66.5, and satisfactory results were obtained.

In addition, the photosensitivity measures, the hydrolysis measures (addition of carbodilite LA-1), and the countermeasures for photodegradation and the hydrolysis measures were used in combination, and the results of the improvement of the transmittance and the sand impact strength of the weather resistance test for 300 hours were compared.

The countermeasure against photodegradation was that the initial physical properties of the sand impact strength and the transmittance were high, and the weather resistance test was hardly reduced for 300 hours.

The hydrolysis countermeasure is that the initial physical properties of the sand blast impact strength and the transmittance are high, and the transmittance for the weather resistance test for 3,000 hours is hardly lowered, but the sand blast impact strength is largely lowered.

The combination of the photodegradation countermeasure and the hydrolysis countermeasure is that the initial physical properties of the sand impact strength and the transmittance are high, and the weather resistance test is hardly reduced for 300 hours. Further, the tensile properties were also improved, and the weather resistance test was promoted for almost 300 hours, and satisfactory results were obtained.

It is understood that this is not only a combination of the countermeasure for photodegradation and the countermeasure for hydrolysis, but an additional effect of high weather resistance can be obtained by the synergistic effect of the countermeasure against photodegradation and the countermeasure against hydrolysis.

The poly(trimethylene terephthalate) cyclohexyl dimethylene methyl ester copolyester is prepared by containing a UV absorber composed of benzoxazinone and a hydrolysis inhibitor composition formed of carbodiimide, and then ejecting A product that is shaped to produce a purpose.

For the ultraviolet absorber formed by the benzoxazinone compound, Add 0.25 to 0.5% by weight of UV absorber "UV-3688" manufactured by SciTech Industries. The benzoxazinone-based compound is described in JP-A-2005-507006, JP-A-2006-182980, and JP-A-2001-055391. These compounds are also available.

The hydrolysis inhibitor of carbodiimide was added to 0.25 to 0.5% by weight of "LA-1" manufactured by Nisshinbo Chemical Co., Ltd. This is a compound described in the specification of Patent No. 3122485 and Patent No. 3388990.

Although it is not included in the above-mentioned main treatment as a treatment means, it is effective to use these means in combination with an antioxidant and a heat resistant material. The treatment with antioxidants and heat resistant materials is as follows.

Tritan TX1001 was treated with the addition of a 0.45% by weight antioxidant of BASF's hindered phenolic antioxidant Irganox 1010.

Irganox 1010 is a representative phenolic antioxidant that exerts an effect on the heat resistance of all resins and elastomers.

When more excellent processing heat stability is required, a phosphorus-based or lactone-based heat stabilizer is used in combination, and the hindered phenol-based antioxidant Irganox 1010 is added with an oxidizing agent of 0.45%. Originally, Irganox 1010 is a high molecular weight, so it is low in extractability and low in volatilization, so it can be used on a wide range of thin to thick objects.

In the aforementioned Tritan TX 1001, a phosphorus-based processing heat stabilizer Irgafos 168 of BASF Corporation was added to 0.15%, and it was used as a heat-resistant treatment agent. Irgafos 168 is a phosphorus-based processing stabilizer that has a strong position as a processing stabilizer. High purity, excellent hydrolysis resistance, and resistance to volatility Sex.

It can be used for a variety of resins such as polyolefin, styrene, polycarbonate, polyester, and polyamide. Irgafos 168, a poly(p-phenylene terephthalate) copolymer of polyester, is used as a heat treatment agent. It is generally recommended to be combined with phenolic antioxidants.

The test method for confirming the effects of the present invention will be specifically described below. The test method is not limited to this method, and if the test result can be confirmed, it can be used as a measurer who can do enough evaluation.

The shape of the test piece used in each test is shown in Fig. 1.

The dumbbell type test piece 11 is 20 mm in width and 150 mm in length.

The 3-stage plate type test piece 12 is 20 mm in width and 150 mm in length.

(1) Drug resistance test

The drug resistance test was carried out in accordance with "Plastic - Test Method for Impregnation Effect of Liquid Drugs" (JIS K 7114). The test piece (area 60 mm × 60 mm, thickness 1.0 mm to 1.1 mm) was immersed in a predetermined reagent solution (test solution temperature 23 ° C ± 2 ° C), and taken out after a predetermined time (20, 200, 2000 hours). The quality, size, and appearance of the test piece before and after the immersion were confirmed.

(2) Weathering test

The weathering test was conducted in accordance with the "Plastic - Exposure Test Method for Laboratory Light Sources (JIS K 7350-2)".

The test piece (dumbbell type and three-stage plate type) was mounted on a weather-resistant tester (Suga Test Machine Co., Ltd. Super Xenon Weatherability Meter SX-75, Fig. 2) with a xenon lamp 23 as a light source to control The disk 22 was set to conditions and an experiment was performed.

After a predetermined period of time (100, 200, 300 hours), the test piece was taken out, and the physical properties of the test piece before and after the weather resistance test were confirmed by the following evaluation test (described in (3) to (8) below). The change in value. The operating conditions of the test machine are equipped with an external light filter, no temperature control inside the tank, the humidity in the input tank is 50±5%, and the black panel is 63±3%. Further, when there is a rain test in the rain, the cycle of the water spray by the water spray port 24 is set to 18 minutes and the spray is stopped for 102 minutes.

Moreover, in the test of the automobile which is often placed in an outdoor environment, the weather resistance test was evaluated to be equivalent to one year in 2000 hours, and 85% of the initial characteristics after 2000 hours was considered to be no problem. The helmet is not often placed in an outdoor environment, and the transmittance is maintained after 300 hours, and the sand impact strength is considered to be weather resistant.

(3) Color difference measurement

The color difference measurement was carried out according to the "Test method for optical properties of plastics (JIS K 7105)" (Fig. 3).

The test piece (the dumbbell type and the three-stage plate type) was placed at an arbitrary position under the measuring head of the color difference measuring device (CM-508 d.31 manufactured by Minolta Co., Ltd.), and the measuring head was placed on the measuring surface of the test piece. The surface color (L ^* a ^* b ^* color shape) of the test piece was measured by a spectrophotometry (SCE) at a light source D65 at a viewing angle of 2°. The color difference ΔE ^* ab of the surface color of the test piece after the weather resistance test was promoted was evaluated based on the surface color of the test piece which was not subjected to the weather resistance test.

Moreover, the color difference measurement value of 3 or more is a limit value which visually feels discoloration.

(4) Gloss measurement

The gloss measurement was carried out in accordance with the "Test method for optical properties of plastics (JIS K 7105)" (Fig. 4).

The test piece (the dumbbell type and the three-stage plate type) was placed on the stage 42, and the measurement head of the gloss meter (GM-60 manufactured by Minolta Co., Ltd.) was placed on the measurement surface of the test piece to measure the gloss (60 degrees). Specular gloss).

(5) Determination of visual transmittance

The visual transmittance measurement was carried out in accordance with the "Test method for optical properties of plastics (JIS K 7105)" (Fig. 5).

The test piece (dumbbell type and three-stage plate shape) was set at the test piece setting position before the light receiving portion of the automatic recording spectrophotometer (Hitachi High-performance Hitachi spectrophotometer U-4100) at a scanning rate of 600 nm. /min, sampling interval 1.00 nm, measuring the spectral transmittance of the wavelength range 380 nm to 780 nm (53). The measured spectral transmittance was converted into (visual) light transmittance (using a conversion formula of JIS T8147), and this was confirmed.

Moreover, in the specification of the glasses, the transmittance of the lens is set to be 85% or more, so that the transmittance is 85% or more, which is an acceptable boundary.

(6) Tensile test

The tensile test was carried out in accordance with "Testing methods for plastic-tensile properties, Part 2: Test conditions for mold forming, extrusion molding, and molded plastic (JIS K 7162)" (Fig. 6).

The test piece (dumbbell type) was placed on a chuck 63 and a lower chuck 63 on the upper portion of a tensile tester (RTC-1310A, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and then placed in a test machine. The lower chuck 63 was moved downward at a speed of 50 mm/min until the test piece was broken. Confirm tensile stress, tensile yielding Change, tensile strain at break.

(7) Bending characteristics test

The bending property test was carried out according to the "Plastic-bending property method (lIS K 7171)" (Fig. 7).

The test piece (the both ends of the test piece for cutting the dumbbell type was processed into 80 × 10 × 2 mm) was placed on a support table 73 (the distance between the fulcrums was 34 mm) of a bending test machine (RTC-1310A, manufactured by Toyo Seiki Seisakusho Co., Ltd.). In the weather resistance test, the face with the illuminating light is turned upward. The test piece was pressed from above with a pressure piece 73 at a speed of 1 mm/min to be deformed. Confirm the bending strength and the bending elastic modulus.

(8) Satay impact strength test

The sand blast impact strength test was carried out in accordance with the "Plastic-sand impact characteristics - Part 1: Non-packaged impact test (lIS K 7111-1)" (Fig. 8).

The test piece of the bell type was processed into the shape of ISO I79/IeA in advance (the both ends of the test piece of the cut-off type) were processed to be 80 × I0 × 2 mm, and the center was subjected to slit processing). The test piece was placed on a support table 83 of a sand hammer impact tester (DG-CB manufactured by Toyo Seiki Co., Ltd.), and the hammer was impacted at a 150° angle with a hammer of 4.00 J. .

In addition, the sand impact strength is defined as a qualifying line by setting the value after the weather resistance test to 90% or more of the initial physical properties.

The test results of the confirmation effect are described below. The invention is not limited thereto. The % in the description is, if not indicated, the weight %.

[Example 1] a. Use of a photodegradation preventing agent as a weathering agent

The photo-deterioration preventing agent may be a case where light is grasped by an ultraviolet ray preventing agent and a case where infrared rays are to be considered. When it is grasped by an ultraviolet ray preventive agent, many preventive agents are known.

UVa (Novapex U to 110 Mitsubishi Chemical Corporation), UVb (manufactured by Irganox BAS F Co., Ltd.), UVc (made by Seesorb 706 White Rock Calcium Co., Ltd.) is in chromatic aberration, transmittance, sand impact strength, tensile breaking strength If the result is not satisfactory, it is judged that there is no effect.

The ultraviolet absorber UV-3638 (manufactured by Sun Chemical Co., Ltd.) of the oxazinone compound has no decrease in transmittance, and has no change in the impact of the sand sputum, and it is judged that it can be effectively used as a photodegradation preventing agent.

Although there is no problem at the point of the strength of the love Cao Te, the conclusion is that it cannot be used alone. The use of the photodegradation preventing agent cannot be a major factor.

[Embodiment 2] b. Utilization of hydrolysis inhibitors as weathering agents

It is still unclear whether a substance having stability of Tritan or the like is liable to cause a hydrolysis reaction under the conditions of use. On the other hand, the use of an ester-bonded poly(terephthalic acid) cyclohexyl dimethylene methyl ester copolyester in the presence of water depends on the environmental conditions and has a hydrolyzable nature, so there is a need Take measures to prevent hydrolysis. For example, only water or acid is present, and there is almost no hydrolysis at normal temperature or low temperature, but in a high-temperature and high-humidity environment, only water will be hydrolyzed, and in the presence of an alkali component, it is considered to be affected by its concentration. And the effect of temperature accelerates hydrolysis.

(a) Adding Nisshinbo Chemical Co., Ltd. to Tritan TX1001 Carbodilite 5% diluted E pellets.

When E pellets are added to TX1001, in the initial state, TX1001 and PET are not uniformly mixed to cause turbidity, and the permeability is poor (transmittance is 80% up and down), and there is a slight yellowing. Therefore, the chromatic aberration and the transmittance cannot be satisfactorily obtained, but the promotion is promoted. The color difference and the transmittance of the weather resistance test for 300 hours were hardly lowered, and it was found to be effective for weather resistance.

(b) Next, in the Tritan X1001, the carbodilite of Nisshinbo Chemical Co., Ltd. was added in a powder form of LA-1 by 0.5%.

When LA-1 was added to TX1001, the decrease in transmittance due to turbidity when E pellets were added was not observed, and the transmittance when TX-1 was added to TX1001 was 90% compared with the transmittance of TX1001. Satisfactory results can be obtained.

This means that when hydrolysis is caused, the ester bond is cut to absorb light, and the transmittance is lowered, so that hydrolysis is not caused.

In the sand blasting test, the initial physical property was NB (no break), but it decreased drastically after 100 hours, and satisfactory results could not be obtained. This is considered to be because the molecular chain is cut by ultraviolet rays.

The effect of giving Tritan is that although there is no problem at the point of transmittance, the low strength of the sand sputum is a problem, and it is concluded that the hydrolysis inhibitor cannot be the main cause.

[Example 3] Use of heat inhibitor as a weathering agent

Heating will activate the substance, so the heating operation will be effective. However, prevention of heating contributes to the stability of the substance. Also a lot. A photo-deterioration inhibitor and a hydrolysis inhibitor are used as a substance for heating as a substance having a stability such as Tritan, and the results are verified.

Next, the photodegradation measures (addition of UV3638 manufactured by Sun Chemical Co., Ltd.), the hydrolysis countermeasure (addition of carbodilite LA-1), and the combination of the countermeasures for deterioration and the countermeasures for hydrolysis were compared as follows.

The countermeasure against photodegradation was that the initial physical properties of the sand impact strength and the transmittance were high, and there was almost no decrease in the weather resistance test for 300 hours.

The hydrolysis countermeasure was high in the initial physical properties of the sand impact strength and the transmittance, and the transmittance was hardly observed after 300 hours of the weather resistance test, but the sand impact strength was greatly lowered.

On the other hand, the combination of the photodegradation countermeasure and the hydrolysis countermeasure was that the initial physical properties of the sand impact strength and the transmittance were high, and the weather resistance test was hardly observed for 300 hours. Further, the tensile properties were also improved, and almost no decrease was observed in the weather resistance test for 300 hours, and satisfactory results were obtained.

In addition, it is said that the photo-deterioration measures and the hydrolysis measures are simply combined, and an additional effect of high weather resistance (heat-preventing agent) can be obtained by the synergistic effect of the photo-deterioration countermeasure and the hydrolysis countermeasure.

According to the above results, it is possible to obtain a transparent resin composition which is stable and has weather resistance and chemical resistance under natural environmental conditions or under the stricter use conditions, and is characterized in that it is polyparaphenylene. The formic acid-extended cyclohexyldimethylene copolyester contains an ultraviolet absorbing agent composed of a benzoxazinone-based compound and a hydrolysis inhibitor composed of carbodiimide.

[Example 4]

Although it does not become the main process mentioned above as a processing means, it is confirmed that it is effective using the antioxidant and heat-resistant material processing.

The treatment using the antioxidant and the heat-resistant material was as follows: Tritan TX1001 was treated as an antioxidant by adding 0.45% of the hindered phenol-based antioxidant Irganox 1010 of BASF Corporation. Irganox 1010 is a representative phenolic antioxidant that can improve the heat resistance of all resins and elastomers.

When more excellent processing heat stability is required, a phosphorus or lactone-based thermal stabilizer is used in combination. Treated with the addition of a hindered phenolic antioxidant Irganox 1010 0.45% antioxidant. Irganox 1010 is a high molecular weight and has low extraction and low volatility, so it can be used in a wide range from thin materials to thick materials.

In the Tritan TX1001, the phosphorus-based processing heat stabilizer Irgafos 168 of BASF Corporation, which is a heat-resistant treatment agent, was added and used in an amount of 0.15%. Irganox 168 is a phosphorus-based processing stabilizer that has a strong position as a processing stabilizer. It is excellent in purity, hydrolysis resistance, and resistance to volatility.

A variety of resins such as polyolefin, styrene, polycarbonate, polyester, and polyamide can be used. A polytrimethylene terephthalate dimethylene methyl ester copolyester of Irganox 168 to polyester can be used as a heat resistance treatment agent. It is generally recommended to be used in combination with phenolic antioxidants.

[Example 5]

Using the transparent resin composition, a helmet can be obtained, and the surface for the helmet can be obtained. A cover, an eyeglass lens, an eyeglass frame and a handle, an outer case for storing articles, a plate for exterior arrangement, and a gear for small and precise gears having lubricating properties.

The test method of the results obtained in other specific examples is shown below.

Environmental stress fracture test (Fig. 9)

In the environmental stress fracture test, the test piece (dumbbell type) was attached to the strain gauge jig 93 by the holder 91. The strain gauge jig 93 has a semi-circular type of cross section, and the curved surface is designed to have a constant bending strain (1.0%) in the center portion of the test piece to be fixed (top view).

The test method is to reverse the strain gauge clamp (below) and place it in the concave portion of the medicine container 94. The drug was placed in the concave portion of the drug container, and the test piece was placed in contact with the drug 95 at room temperature for 3 hours. After the test piece was taken out and thoroughly washed and dried, the quality, size, and appearance of the test piece before and after the immersion were confirmed. As a result of the test, the tensile strain at break (tensile fracture strain, tensile elongation at break) was also confirmed in the test piece which was not broken. The test method was carried out in the same manner as in the (6) tensile test, in accordance with "Testing methods for plastic-tensile properties, Part 2: Test conditions for mold forming, extrusion molding, and molded plastic (JIS K 7162)". The test piece (dumbbell type) was clamped by an upper jig and a lower jig of a tensile tester (RTC-1310A, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and fixed to a test machine. The lower jig was moved downward at a speed of 50 mm/min until the test piece was broken, and the tensile strain at break was confirmed. The influence on the drug which did not appear in appearance was confirmed by the measurement of elongation at break.

In the test piece of the same material, the elongation at break of the test piece which was not subjected to the pretreatment such as contact with the drug was set to 100, and the elongation at break of the test piece which was subjected to the pretreatment such as contact with the drug was expressed in %, as follows. Standard Quasi-assessment.

◎: 85% or more

○: 70% or more and less than 85%

△: 30% or more and less than 70%

×: Less than 30%, tensile test cannot be performed due to breakage

Grade 1 assessment when there is whitening, yellowing or fogging

The environmental stress fracture test is one of tests for confirming environmental stress fracture (environmental stress cracking). The environmental stress fracture is a drug that has no effect on the adhesion of a certain resin or has little influence, and is attached to the drug in a state where a force is applied (a force applied from the outside such as internal stress or a joint stress during molding). The breakage will affect or increase the impact in a short period of time. The fracture caused by the force and the drug applied as described above is called environmental stress fracture. This test confirms the presence or absence of environmental stress fracture.

In addition, this test is to set very harsh conditions in order to make the resistance of the resin poor. Under actual conditions of use, it is difficult to imagine a situation in which the drug is continuously impregnated for 3 hours. Moreover, the environmental stress fracture is the greater the impact of the force. In the case of polycarbonate, the internal stress of the test piece was estimated to be 23 MPa when subjected to a strain of 1.0%. According to the resin manufacturer's data, the residual stress of 8.3 Mp is regarded as "the strain check when the molded product is a single body", and a force much larger than this is applied.

The polybutylene terephthalate dimethylene methyl ester copolyester resin of the present inventors was confirmed to have physical properties and environmental stress fracture of Tritan (trade name). The result is as follows.

From the above results, it was confirmed that the physical property data shown by the environmental stress fracture test of the poly(ethylene terephthalate) cyclohexyldimethylene copolyester resin was good and resistant.

The weather resistance test was carried out by the above-mentioned test method (described in the above (2) to (8)), and the change in the physical property value of the test piece before and after the weather resistance test was confirmed. Moreover, in the test of an automobile which is often placed in an outdoor environment, it is considered that 2000 hours of the weather resistance test is equivalent to 10 years, and 85% of the initial characteristics after 2000 hours is considered to be no problem. When it is not always placed in a helmet in an outdoor environment, it is considered to have weather resistance after maintaining the transmittance and the sand impact strength after 300 hours.

[Embodiment 7] a, the trial works of halving the weathering agent

The formulation with improved weather resistance is 0.5% UV absorber UV-3638 and 0.25% hydrolysis inhibitor carbodilite LA-1. When the amount of each addition was halved, and each of them was 0.25% and 0.125%, the weather resistance was examined. The coloring was white, transparent blue, and transparent green (White, C-Blue, C-Green), and the standard amount (T1) was added, and the amount added was halved (T2), and evaluated.

As a result, the tensile strain at break of the trial works in which the amount of addition of the three colors was halved was lowered. The result of the white sand smashing test is NB. In the half-tested addition, the weather resistance test broke at 200 hours. Although the weathering agent halved test works have a certain degree of weather resistance, the weather resistance can be said to be worse than the standard amount of the test work.

[Embodiment 8]

Agent change

The white color material in the trials so far is titanium oxide ((White T2). For comparison, the difference in weather resistance of the test piece (White T3) colored with zinc sulfide was examined. The second test before the weather resistance test was carried out. There was no difference in the results. After the weather resistance test was carried out, there was a good result of coloring titanium oxide on the color difference. The tensile strain at break and the impact strength of the sand have good results in coloring with zinc sulfide.

[Embodiment 8] c, halving the color material

The difference in weather resistance of the half-tested work (blue T2) of the toner for the blue-colored colorant standard test piece (Blueing T1) was examined. Both get results with weather resistance.

In the above comprehensive evaluation, when there is a mark of ○, it indicates that there is a good result. Also, the presence of △ indicates that there is no problem in use.

Γ-ray sterilization test

Poly in polycarbonate and weather resistant Tritan (TX 2001 Blueing T1) Test piece of carbonate and weather resistant Tritan (TX 2001 Blueing T1) (4 cm × 4 cm plate shape, thickness 1.5 mm) and Tritan virgin (TX2001) test piece (2 cm × 4 cm plate shape, thickness 4 mm), using γ line The irradiation facility (Radie Industrial RIC-1 (No. 1)) irradiates the γ line. After the irradiation of the predetermined absorption line amount (10 kGy, 20 kGy), the test piece was taken out, and the change in the physical property value of the test piece before and after the γ-ray irradiation sterilization was confirmed by the above-described evaluation test (described in the above (3) to (5)).

Each of the glasses made of Tritan was sterilized by gamma ray and evaluated for each purpose.

The shape of the test piece was polycarbonate, and the weather resistant Tritan (T1) was a plate shape of 4 cm × 4 cm and a thickness of 1.5 mm. The Virgain Tritan is 2 cm x 4 cm and has a thickness of 4 mm.

Polycarbonate and weathering Tritan before and after gamma irradiation sterilization have different thicknesses, but TritanVirgin as a reference value is determined by Konica Minolta color difference meter CR-300, light source D65, and the viewing angle is 2°, and the gamma line is obtained. The color difference between the irradiated lens and the new lens. The lens was transparent, so the white plate was placed underneath and measured.

Compare existing polycarbonate lenses with tried-and-tested Tritan lenses (T1) with additives. Divine's Virgin pellet-formed dumbbell-shaped test piece was measured as a reference value although the thickness was different.

Polycarbonate also has significant discoloration at 10KGy. TritanVirgin is also almost discolored at 20kGy. The weather-resistant Tritan is slightly discolored at 10kGy, and the degree of discoloration at 20kGy.

Polycarbonate is sterilized by 20 kGy gamma rays and its visual transmittance is reduced by 1.6%. Weathering Tritan and Tritan Virgin are visually sensitized after gamma sterilization The transmission rate is maintained and the original value is maintained.

Tritan and the weathering agent used are unaffected by the influence of gamma rays on polycarbonate.

From the above, as shown in the following table, it was confirmed that Tritan has good physical properties and is resistant to γ linearity.

(11) UV transmittance test

The test was carried out in accordance with the "Test Method for Optical Properties of Plastics (lIS K 7105)".

The test piece (the dumbbell type and the three-stage plate type) is placed at the test piece setting position (glass lens) before the light receiving portion of the automatic recording spectrophotometer (Hitachi High-performance Hitachi Spectrophotometer U-4100, manufactured by Hitachi High-Tech Co., Ltd.), The spectral transmittance was measured at a scanning speed of 600 nm/min, a sampling interval of 1.00 nm, and a wavelength range of 380 nm to 780 nm. The measured spectral transmittance was converted into a (visual) transmittance (using a conversion formula of JIS T8147) and confirmed.

P _cλ : the spectral distribution value of the standard light source A

V (λ): the standard-to-visual sensitivity of the visual field in the 2 degree field of view

T (λ): test filter Spectral transmittance

Tv : visual transmittance (%)

Further, in JIS T 8147:2003 "goggles", the lens having the goggles has a visual transmittance of 85% or more, so that the transmittance is 85% or more as a qualified boundary.

The test piece was prepared by adding UV-3638: 0.5%, LA-I: 0.25% to TX2001, and performing color fine adjustment (blue: blueing). T2 is to halve the color fine adjustment (blue: blueing) from T1.

The visual transmittance is that the visible light (visible light) of the eye ranges from 380 nm to 780 nm, but the human eye has different sensitivities due to the wavelength (green or yellow light of the same intensity will be bright, purple or red). Light will feel dark). The transmittance of a wavelength higher than the visual sensitivity is emphasized, and the transmittance of the wavelength lower than the visual sensitivity is despised to be weighted and averaged. The visual transmittance is 100% colorless and transparent.

Ultraviolet light is light having a shorter wavelength than visible light (380 nm or less). Harmful to the eyes and cause keratitis or cataracts. Although the goggles are not specified in JIS, it is ideal for imperviousness.

Polycarbonate is used as a lens material for goggles because of its high visual transmittance and almost no transmission in the ultraviolet field.

TritanVirgin has a high visual transmittance and passes through the ultraviolet field, but the weather resistant Tritan has a high visual transmittance and almost no UV transmission. When Tritan added a weathering agent, the utilization value of the lens material of the goggles can be improved.

[Industrial availability]

The present invention can provide a transparent resin composition which is extremely stable and has stability and resistance to weathering under the natural conditions or under the stricter use conditions, and can promote a wide range of utilization.

11‧‧‧Test piece (dumbbell type)

12‧‧‧Test piece (3-stage plate type)

21‧‧‧Test piece assembly board

22‧‧‧Control panel

23‧‧‧氙Lights

24‧‧‧Water spray

31‧‧‧Measurement device

32‧‧‧Test strips

41‧‧‧Gloss meter

42‧‧‧ test piece

51‧‧‧ Monochromatic light irradiation port

52‧‧‧Test strips

53‧‧‧Receiving Department

61‧‧‧Packed sample containers

62‧‧‧ test piece

63‧‧‧Clamp

71‧‧‧Loading sample containers

72‧‧‧ test piece

73‧‧‧Press

74‧‧‧Support table

81‧‧‧imping blade

82‧‧‧ test bench

83‧‧‧Support table

91‧‧‧Retainer

92‧‧‧ test piece

93‧‧‧ Fixed strain gauge

94‧‧‧Drug tank

95‧‧‧ drugs

Fig. 1 (a) and (b) show test pieces for performance.

Fig. 2 shows an apparatus for promoting a weather resistance test.

Figure 3 shows the apparatus for the color difference measurement test.

Figure 4 shows the apparatus for the gloss measurement test.

Figure 5 shows the device for the full light transmittance test.

Figure 6 shows the tensile test apparatus.

Figure 7 shows the apparatus for the bending property test.

Figure 8 shows the apparatus for the sand impact strength test.

Figure 9 shows the apparatus for the environmental stress crack test.

Fig. 10 shows the results of measurement of the visual transmittance.

Fig. 11 shows the results of measurement of total light transmittance.

Since the picture in this case is a test device, it is not a representative figure of this case. Therefore, there is no designated representative map in this case.

Claims (9)

A natural environment under the conditions of sunlight, rain or washing water, atmospheric pollutants, oxygen in the air, high temperature, high humidity or low humidity irradiated by sunlight, and under such harsh natural environmental conditions. Or a transparent resin composition which is stable and has weather resistance and chemical resistance under the same severe conditions, and is characterized by being selected from Tritan (registered trademark) "TX1000", "TX1001", "TX1500HF". The resin of at least one of "TX2000" and "TX2001" contains 0.25 to 2.5% by weight of a UV absorber composed of a benzoxazinone compound and a hydrolysis inhibitor 0.125 from carbodiimide. Up to 0.5% by weight. As described in the first paragraph of the patent application, under the natural environment conditions of sunlight, rain or washing water, atmospheric pollutants, oxygen in the air, and high temperature, high humidity or low humidity in the sunlight. And a transparent resin composition which is stable and has weather resistance and chemical resistance under the harsh natural environmental conditions or under the stricter use conditions, and further contains an antioxidant and/or a heat resistant material. As described in the second paragraph of the patent application, under the natural environment conditions of sunlight, rain or washing water, atmospheric pollutants, oxygen in the air, and high temperature, high humidity or low humidity under the sunlight. And a transparent resin composition which is stable and has weather resistance and chemical resistance under the harsh natural environment conditions or under the stricter use conditions, wherein the antioxidant is a hindered phenol-based antioxidant, The heat resistant material is a phosphorus-based processing heat stabilizer. A safety helmet characterized by using sunlight, rain water or washing water, air pollutants, oxygen in the air, and the sun as described in any one of claims 1 to 3. Transparent under the natural environment conditions of high temperature, high humidity or low humidity under light irradiation and under such harsh natural environmental conditions or under the stricter conditions of use, it is transparent and weather resistant and resistant. Manufacturer of resin composition. A mask for a safety helmet, characterized in that the use of sunlight, rain water or washing water, atmospheric pollutants, oxygen in the air, as described in any one of claims 1 to 3, It is stable and weather resistant and resistant under natural environmental conditions in a high temperature, high humidity or low humidity environment exposed to sunlight and under such harsh natural environmental conditions or under the stricter conditions of use. Manufacturer of transparent resin composition. A lens for spectacles, characterized in that the use of sunlight, rain water or washing water, atmospheric pollutants, and oxygen in the air as described in any one of claims 1 to 3, It is stable and weather resistant and resistant under natural environmental conditions in a high-temperature, high-humidity or low-humidity environment exposed to sunlight and under such harsh natural environmental conditions or under the stricter conditions of use. Produced by a transparent resin composition. An outer casing for storing articles, characterized in that the use of sunlight, rain water or washing water, atmospheric pollutants, and oxygen in the air as described in any one of claims 1 to 3, With the sun Transparent resin with weather resistance and resistance under natural environmental conditions in a high temperature, high humidity or low humidity environment and under such harsh natural environmental conditions or under the stricter conditions of use The composition is manufactured by the manufacturer. A sheet for exterior distribution, characterized in that the use of sunlight, rain water or washing water, atmospheric pollutants, oxygen in the air, as described in any one of claims 1 to 3, It is stable and weather resistant and resistant under natural environmental conditions in a high temperature, high humidity or low humidity environment exposed to sunlight and under such harsh natural environmental conditions or under the stricter conditions of use. Manufacturer of transparent resin composition. A spectacles or a spectacles for spectacles, characterized by using sunlight, rain water or washing water, atmospheric pollutants, oxygen in the air according to any one of claims 1 to 3. Existence and weatherability under natural environmental conditions in a high temperature, high humidity or low humidity environment exposed to sunlight and under such harsh natural environmental conditions or under the stricter conditions of use and Produced by a resistant transparent resin composition.