JP2005028796A - Transparent flame-retardant vinyl chloride-based resin laminate having hot water whitening resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin molded object having transparency, flame retardancy and processability and withstanding hot water immersion. <P>SOLUTION: The transparent flame-retardant vinyl chloride-based resin laminate comprises a vinyl chloride resin-based composition and has at least a base layer and a surface layer. The base layer comprises a resin composition having transparency and flame retardancy and the surface layer comprises a resin composition which has hot water whitening resistance and of which the total light transmissivity, after the laminate is immersed in hot water at 80°C for 24 hr, is 50% or above and the haze value is 20% or lower. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a vinyl chloride resin laminate that is transparent, flame retardant, and has excellent hot water whitening resistance.

  Since vinyl chloride resin contains chlorine in the molecule, it is excellent in flame retardancy. Moreover, since various additives can be added in a wide content, a wide range of mechanical properties, heat resistance, moldability, and weather resistance can be realized.

  Since the vinyl chloride resin has the characteristics as described above, the molded product of the hard vinyl chloride resin composition is particularly suitable for interior / exterior materials for transport aircraft such as aircraft, ships, vehicles, etc .; It has been used as daily goods such as office tools; housing materials for home appliances, electronic devices, etc .; parts for semiconductor devices.

  In particular, the laminated material of the present invention is suitable for use as a member in contact with hot water, for example, an industrial member for semiconductor manufacturing equipment. In some cases, warm water is used in a semiconductor cleaning device or the like. If warm water is applied to the inspection window, the partition plate, the member of the liquid recovery tank, etc., the conventional single layer product of chlorinated vinyl chloride resin may be whitened. When blended prescriptions that prevent warm water whitening tend to deteriorate transparency and flame retardancy, improvements have been desired.

  In addition, when vinyl chloride resin is exposed to high temperatures above the heat-resistant temperature due to fire or other reasons, it emits a large amount of smoke due to chlorine in the molecule and generates toxic gases such as chlorine gas and hydrogen chloride gas. To do. For this reason, attempts have been made to suppress the generation of toxic gases by examining the types and amounts of additives.

  For example, Patent Document 1 discloses a molded body in which a surface layer is laminated on at least one surface of a base layer for the purpose of a transparent vinyl chloride resin that satisfies the FM standard, and the surface layer has a chlorination degree (the chlorine content of the resin is expressed by mass). The tin-based stabilizer is a mixed resin having an average chlorination degree of 58 to 60% between a straight vinyl chloride resin of 56.8% and a chlorinated vinyl chloride resin having a higher chlorination degree. A transparent layer composed of a layer containing a tin-based stabilizer in a chlorinated vinyl chloride resin having a chlorination degree (60 to 66%) higher than the average chlorination degree of the mixed resin of the surface layer. A flame retardant vinyl chloride resin molded article is disclosed.

  However, since this does not describe any whitening test after immersion in warm water, in addition to transparency and flame retardancy, it is necessary to combine the properties to withstand immersion in warm water, for example, semiconductor manufacturing using warm water It cannot be estimated whether the device can be used.

  The inventors of the present application have examined the molded body described in Patent Document 1, but this molded body satisfies the flame retardancy, but does not have the property to withstand immersion in hot water. It became clear that this improvement was an important subject when it was found that it could not be used for applications.

  Moreover, in patent document 2, it is the molded object which laminated | stacked the surface layer on the at least single side | surface of the base layer for the purpose of the transparent vinyl chloride resin which satisfy | fills FM specification, Comprising: A foaming agent is added to the surface layer and / or the straight vinyl chloride resin of a base layer. , A transparent flame-retardant vinyl chloride resin molded article comprising a layer using tin malate or a laurate stabilizer by adding at least one of a decomposition accelerator, a radical generator, and a crosslinking agent is disclosed. .

  However, when the molded body is used in an environment where water is used, particularly in an environment where warm water (60 ° C. or higher) contacts, there is a problem that the transparency is lowered (hereinafter referred to as hot water whitening). In addition, since vinyl chloride resins having different refractive indexes (refractive index: 1.540) and chlorinated vinyl chloride resins (refractive index: 1.550 <chlorination degree 65%>) are mixed, sufficient transparency, especially There was a problem that unevenness at the surface / base layer interface was difficult to improve.

Therefore, in the transparent flame-retardant vinyl chloride resin molded body as described above, although it is transparent and flame-retardant, it does not satisfy the hot water whitening resistance.
JP 2002-210893A JP 2001-341247 A

  In the present invention, there are provided a flame retardant vinyl chloride resin composition excellent in flame retardancy, hot water whitening resistance, thermal stability in molding process and appearance when molded, and a laminate using the same. The purpose is to do.

  The present invention includes the following inventions.

  [1] A flame-retardant laminate comprising a vinyl chloride resin composition and having at least a base layer and a surface layer, the base layer comprising a resin composition having transparency and flame retardancy, Transparent and difficult, characterized in that the surface layer is made of a resin composition having a resistance to whitening with warm water having a total light transmittance of 50% or more after being immersed in warm water at 80 ° C. for 24 hours and a haze value of 20% or less. Flammable vinyl chloride resin laminate.

  [2] The transparent and flame-retardant vinyl chloride according to [1], wherein the thickness of the base layer is at least 1 mm or more, and the thickness of the surface layer is 0.05 mm or more and 2 mm or less -Based resin laminate.

  [3] The base layer is composed of one or more chlorinated vinyl chloride resins having a chlorination degree of 57.0% or more and less than 71.0%, and has an average chlorination degree of 62.0% or more and 68.0% or less. The transparent and flame-retardant vinyl chloride resin laminate as described in [1] or [2].

  [4] Mixing a chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 60.0% with a chlorinated vinyl chloride resin having a chlorination degree of 60.0% or more and less than 71.0%. The transparent and flame-retardant material according to any one of [1] to [3], wherein a chlorinated vinyl chloride resin composition having an average chlorination degree of 58.0% or more and less than 62.0% is used. A vinyl chloride resin laminate.

[5] Any of [1] to [4], wherein the average calorific value (AHRR) and average dimming volume (ASEA) measured in accordance with ASTM E1354 are 65 kW / m ² or less and 800 m ² / g or less, respectively. A transparent and flame retardant vinyl chloride resin laminate according to claim 1.

  According to the present invention, it is possible to provide a molded body that can withstand transparency, flame retardancy, processability, and hot water immersion.

  Hereinafter, preferred embodiments of the present invention will be described.

  As the vinyl chloride resin in the present invention, chlorinated vinyl chloride resin, chlorinated vinyl chloride-ethylene copolymer, chlorinated vinyl chloride-vinyl acetate copolymer, chlorinated vinyl chloride-acrylic copolymer, etc. Can be used.

  There are straight vinyl chloride resins (chlorination degree of about 56.8%) as vinyl chloride resins, but when they are mixed, the softening temperature decreases and it is difficult to ensure high warm water whitening (for example, hot water temperature is 80 ° C). .

  The mixed system of straight vinyl chloride resin and chlorinated vinyl chloride resin tends to be a micro-inhomogeneous mixed system because the peak of loss tangent (Tanδ) measured according to JIS K 7198 has a two-peak distribution. Therefore, it is difficult to achieve high transparency due to the difference in refractive index. Also, when mixing ordinary straight vinyl chloride resin and chlorinated vinyl chloride resin, it is difficult to ensure high warm water whitening property because warm water penetrates from the micro uneven mixing interface, so mixing of chlorinated vinyl chloride resins is effective. It is.

  The distribution of loss tangents here means that the loss tangent curve of the mixture peaks at two positions, the peak position of the loss tangent curve of the vinyl chloride resin only and the peak position of the loss tangent curve of the chlorinated vinyl chloride resin only. Is a composition of each peak, and has a point of inflection near the loss tangent curve value of each peak. If the loss tangent curve of the mixture has a bimodal distribution, it is determined that an incompatible polymer alloy is formed by the two types of resins. The state of incompatibility does not mean that the phases are completely separated, but the state in which the chlorinated vinyl chloride resin and the straight vinyl chloride resin are substantially phase-separated. It also includes a state in which a melted portion exists. The state of this incompatible polymer alloy is described as a micro-heterogeneous mixed state. Further, since the incompatible polymer alloy generally has a plurality of glass transition temperatures, the same argument can be made in that there are two or more temperatures at which softening proceeds rapidly.

Chlorinated vinyl chloride forms a straight vinyl chloride resin obtained by polymerization with a particle structure, and then applies light in a slurry state or heats it or heats it while applying light to add chlorine. Since vinyl chloride resin has a wider distribution of chlorine than vinyl chloride resin, it is not only a difference in chlorination degree but also a different chlorine distribution. (Reference: Nikkan Kogyo Shimbun, Polyvinyl Chloride-Fundamentals and Applications, p168-182)
Among the chlorinated vinyl chloride resins, a technology to make the chlorine present in the resin particles uniform is being studied. Chlorinated vinyl chloride chlorinated by thermal chlorination rather than photochlorination. The resin is preferred for use because of its uniform chlorine distribution. It seems that the mixture of straight vinyl chloride resin and chlorinated vinyl chloride resin becomes non-uniform, which tends to have an adverse effect on transparency and whitening of hot water, and the mixture of chlorinated vinyl chloride resins becomes uniform. This seems to be the cause of the difference between various phenomena.

  As the stabilizer, a tin-based stabilizer is used because transparency cannot be ensured with a lead-based stabilizer. In general, among the tin stabilizers in the vinyl chloride resin, the mercapto type is advantageous for transparency and warm water whitening, but the softening temperature is lowered and the flammability tends to be hindered. Malate and laurate systems have transparency and warm water whitening properties, but are less likely to hinder softening temperature and flammability. However, since flammability is dominated by the chlorinated vinyl chloride resin itself, in the chlorinated vinyl chloride resin, mercapto is advantageous for transparency and warm water whitening, but the softening temperature tends to be lowered. In addition, malate and laurate are inferior in transparency and warm water whitening, but hardly inhibit the softening temperature. Therefore, one or more types can be combined and used in consideration of these features. For example, in the chlorinated vinyl chloride resin as in the present invention, it is advantageous to use any one of tin mercapto based on the surface layer and tin mercapto, tin malate and tin laurate on the base layer.

  The transparency mentioned here means that when the thickness is 5 mm, the total light transmittance is 40% or more and the haze value is 60% or more, preferably, the total light transmittance is 60% or more and the haze value is 30% or less. is there.

  Therefore, a tin-mercapto resin is used for the surface layer of a mixed resin of chlorinated vinyl chloride resins, and high hot water whitening resistance can be obtained if the Vicat softening temperature is preferably 76 ° C. or higher.

  The base layer comprises at least one chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 71.0%, preferably 61.0% or more and 69.0% or less, and has an average chlorination degree of 62.0%. % Or more and 68.0% or less, preferably 66.0% or more and 66.0% or less.

  The surface layer is a chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 60%, preferably 58.0% or more and 59.0 or less, and a chlorination degree of 60.0% or more and less than 71.0%, preferably Is an average chlorination degree of 58.0% or more and less than 62.0%, preferably 60.0% or more and 61.0% or less by mixing 63.0% or more and less than 68.0% chlorinated vinyl chloride resin. is there.

  Particularly preferably, 75:25 to 70:30 of a post-chlorinated vinyl chloride resin having a surface layer chlorination degree of about 58.0% and a post-chlorination vinyl chloride resin having a chlorination degree of about 65.0% are mixed in an average chlorination. A chlorinated vinyl chloride resin having a degree of chlorination of 59.8 to 61.1% and a chlorination degree of the base layer of about 65.0% is used.

  Since the degree of chlorination and flame retardancy are positively correlated, the higher the degree of chlorination, the better the flame retardancy. However, since the degree of chlorination, moldability (discoloration and decomposition), and chemical resistance are negatively correlated, the lower the degree of chlorine, the better the moldability, color tone, and chemical resistance. Therefore, if the average chlorination degree is too low, flame retardancy cannot be obtained. On the other hand, if the average chlorination degree is too high, the initial coloring, chemical resistance and molding processability deteriorate.

  The total average chlorination rate of the surface and the base layer is set high in a range where flame retardancy can be secured, the surface layer is directly related to chemical resistance, so the chlorination rate is low, and the base layer is not directly related to chemical resistance, so It is advantageous to increase the conversion rate.

  If the surface layer having a lower chlorination rate than the base layer is one kind of chlorinated vinyl chloride resin, the transparency may decrease due to a change in the refractive index due to a sudden change in the chlorination rate at the interface between the surface layer and the base layer. There is a defect that causes Therefore, better transparency can be obtained by mixing two or more different chlorinated vinyl chloride resins on the surface layer. In that case, when mixed with straight vinyl chloride resin, the refractive index difference of the surface layer itself occurs due to the micro non-uniform mixing system of straight vinyl chloride resin and chlorinated vinyl chloride resin, resulting in lower transparency or unevenness at the surface layer / base layer interface. May occur. Further, it is difficult to obtain a sufficient softening temperature increasing effect, and it is difficult to improve warm water whitening resistance and chemical resistance. Therefore, better transparency and warm water whitening resistance can be obtained by mixing two or more different types of chlorinated vinyl chloride resins in the chlorinated vinyl chloride resin system.

  Next, a predetermined amount of vinyl chloride resin, tin stabilizer, lubricant, impact modifier, processing aid, pigment and the like are mixed using a blender, a Henschel mixer or the like.

  The composition obtained as described above is processed into a flame retardant vinyl chloride resin laminate such as a film, a sheet, a plate material, a pipe, and an odd-shaped article by extrusion molding, calender molding, press molding method or the like.

  The flame retardancy of the flame retardant vinyl chloride resin molded product produced as described above can be evaluated using a cone calorimeter according to ASTM E1354. The flame retardant properties evaluated by the combustion test using a corn calorimeter include the maximum value of calorific value due to combustion per unit area and unit time (maximum calorific value, also referred to as PHRR; unit: kW / m 2), unit area And the average value of calorific value by combustion per unit time (average calorific value, also described as AHRR; unit: kW / m2), total calorific value by combustion (also described as total calorific value, THR; unit: MJ / m2) Average value of mass reduction rate due to combustion per unit area and unit time (also referred to as mass reduction rate, AMLR; unit: g / sec · m 2), maximum value of light reduction volume due to combustion per unit area and unit time (Maximum dimming volume, also described as PSEA; unit: m2 / g), average value of dimming volume due to combustion per unit area and unit time (average dimming volume, ASEA and Described; Unit: m2 / g), and the like.

  Conventionally, as one of the flame retardant indicators, evaluation standards defined by the Factory Mutual Insurance System have been used effectively.

  This evaluation standard was measured based on the flame retardant test (FMRC, Clean Room Materials Flammability Test Protocol) of clean room materials listed as Class Number 4910, and the flame spread index FPI indicating flame retardancy and fuming indicating smoke. An index SDI, a corrosion index CDI indicating the generation of corrosive gas, and the like are used as indexes (also referred to as FM standards).

  In the present invention, instead of the FM standard, a value evaluated by a combustion test using a cone calorimeter is used as an index of flame retardancy. The FM standard is a standard that is obtained by submitting test specimens to an industry mutual insurance organization and evaluating the industry mutual insurance organization, so it takes time to obtain an evaluation result and is inefficient. The combustion test using a corn calorimeter is efficient because it can be performed by the inventors.

  In particular, FPI has a strong correlation with indices related to calorific values such as PHRR, AHRR and THR measured by a corn calorimeter. In addition, SDI has a strong correlation with indicators relating to dimming volume such as PSEA and ASEA. Furthermore, CDI has a strong correlation with an index related to mass loss such as AMLR.

  Therefore, by evaluating the flame retardancy using a corn calorimeter, the approximate value of the FM standard can be obtained efficiently.

  In the FM standard, FPI is 6 or less and SDI is 0.4 or less. In the present invention, PHRR is 130 kW / m 2 or less, AHRR is 82 kW / m 2 or less, THR Are 100 MJ / m 2 or less, AMLR is 13 g / sec · m 2 or less, PSEA is 1500 m 2 / g or less, and ASEA is 1000 m 2 / g or less. Among them, the AHRR and ASEA characteristics are particularly dominant and important.

  Warm water whitening resistance of flame retardant vinyl chloride resin molded products produced as described above is an index indicating the degree of transparency deterioration when used in the temperature range near the upper limit where heat deformation does not occur. It shows that it has the transparency which can endure use even in severe conditions, so that property is favorable. The temperature is the severest condition in the vicinity of the upper limit at which the glassy region of the resin can be manifested (the JISK 7207 load deflection temperature is a guide). At that temperature, the resin itself is softened and deformed, and the molded body itself is not valuable. Further, at a temperature much lower than that temperature, for example, evaluation at normal temperature (23 ° C.) does not reflect the situation under severe conditions. Accordingly, a hard chlorinated vinyl chloride resin having an average chlorination degree of 65% is evaluated at 80 ° C. because it is around 85 ° C.

  The flame retardant vinyl chloride resin composition according to the present invention is characterized by high transparency, excellent flame retardancy, low smoke generation, and good warm water whitening properties.

  Therefore, in particular, the molded body of the hard vinyl chloride resin composition is used for interior / exterior materials for aircraft, ships, vehicles, etc .; interior / exterior materials for buildings; daily goods such as furniture, office tools; home appliances, electronic devices, etc. Housing material; can be suitably used as a component of a semiconductor device.

The present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention. In the examples, raw materials used and evaluation methods are shown below.
Tin stabilizer: Dibutyltin mercaptothioglycolate
STNN JF-10B (manufactured by Sansha Co., Ltd.)
Processing aid: Methyl methacrylate / butyl acrylate copolymer Kaneace PA-20 (manufactured by Kaneka Chemical Co., Ltd.)
Lubricant: Glycerol monostearate / pentaerythritol adipate stearate 3/1 mixture (Ricester EW200, manufactured by Riken Vitamin Co., Ltd.)
Impact modifier: Core / shell modifier
The core is butadiene-styrene copolymer and the shell is styrene / methyl methacrylate copolymer
(Kane Ace B-11A Kaneka Chemical Co., Ltd.)

(Evaluation methods)
(A) Evaluation of flame retardancy: AHRR (kW / m 2) and ASEA (m 2 / g) were measured according to ASTM E1354 using a cone calorimeter manufactured by Atlas.
(A) Transparency: total light transmittance and haze on a 5 mm plate
Visual observation of laminated interface (existence of unevenness)
(C) Evaluation of warm water whitening property: total light transmittance after immersion for 24 hours at 80 ° C., haze (e) Evaluation of chemical resistance: appearance after immersion in 35% sulfuric acid at 60 ° C. for 14 days (presence of cracks)
(E) Evaluation of molding processability: The decomposition time at 200 ° C. was measured by a dynamic thermal stability evaluation method using a plastmill. Decomposition time is the time when the torque starts to increase by more than 10%.

  The experimental results are shown in Table 1.

Claims (5)

A flame retardant laminate comprising a vinyl chloride resin composition and having at least a base layer and a surface layer, the base layer comprising a transparent and flame retardant resin composition, wherein the surface layer comprises It is transparent and flame retardant, characterized by comprising a resin composition having a hot water whitening resistance with a total light transmittance of 50% or more and a haze value of 20% or less after immersion in warm water at 80 ° C. for 24 hours. A vinyl chloride resin laminate. The transparent and flame-retardant vinyl chloride resin laminate according to claim 1, wherein the thickness of the base layer is at least 1 mm or more, and the thickness of the surface layer is 0.05 mm or more and 2 mm or less. body. The base layer is composed of one or more chlorinated vinyl chloride resins having a chlorination degree of 57.0% or more and less than 71.0%, and has an average chlorination degree of 62.0% or more and 68.0% or less. The transparent and flame-retardant vinyl chloride resin laminate according to claim 1. The surface layer is mixed with a chlorinated vinyl chloride resin having a chlorination degree of 57.0% or more and less than 60.0% and a chlorinated vinyl chloride resin having a chlorination degree of 60.0% or more and less than 71.0%, and the average chlorine The transparent and flame-retardant vinyl chloride resin laminate according to any one of claims 1 to 3, wherein a chlorinated vinyl chloride resin having a degree of conversion of 58.0% or more and less than 62.0% is used. . The transparent heat according to any one of claims 1 to 4, wherein an average calorific value (AHRR) and an average attenuation volume (ASEA) measured according to ASTM E1354 are 65 kW / m ² or less and 800 m ² / g or less, respectively. A flame retardant vinyl chloride resin laminate.