阅读说明：本技术 树脂组合物和树脂片 (Resin composition and resin sheet ) 是由 太田崇智 铃木达也 于 2020-04-14 设计创作，主要内容包括：本发明提供一种兼顾优异的耐热性和阻燃性、以及优异的成型性的树脂组合物。本发明涉及的树脂组合物含有丙烯系树脂和/或乙烯系树脂、由下述式(1)或下述式(2)表示的NOR类HALS化合物、以及闪点为360℃以上的磷系化合物。式(2)中,R为下述式(2-1)表示的基团。(The invention provides a resin composition which has excellent heat resistance, flame retardance and excellent moldability. The resin composition according to the present invention comprises a propylene resin and/or a vinyl resin, a NOR-type HALS compound represented by the following formula (1) or the following formula (2), and a phosphorus compound having a flash point of 360 ℃ or higher. In the formula (2), R is a group represented by the following formula (2-1).)

1. A resin composition characterized by comprising:

a propylene resin and/or an ethylene resin,

A NOR-type HALS compound represented by the following formula (1) or the following formula (2), and

a phosphorus compound having a flash point of 360 ℃ or higher,

in the formula (2), R is a group represented by the following formula (2-1),

2. the resin composition according to claim 1, wherein the phosphorus compound is contained in an amount of 0.1 to 7 parts by mass per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin.

3. The resin composition according to claim 1 or 2, wherein the NOR-based HALS compound is contained in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin.

4. The resin composition according to any one of claims 1 to 3, wherein the degree of hydrolysis of the phosphorus-based compound is 10% by mass or less.

5. The resin composition according to any one of claims 1 to 4, wherein the ratio of the content of the phosphorus-based compound to the content of the NOR-type HALS compound is 0.5 to 30 on a mass basis.

6. The resin composition according to any one of claims 1 to 5, wherein the phosphorus-based compound comprises a phosphite compound and/or a phosphate compound.

7. The resin composition according to any one of claims 1 to 6, wherein the resin composition contains an inorganic filler.

8. The resin composition according to any one of claims 1 to 7, wherein the resin composition contains at least a propylene-based resin.

9. A resin sheet comprising a layer formed using the resin composition according to any one of claims 1 to 8.

Technical Field

The present invention relates to a resin composition and a resin sheet molded using the resin composition.

Background

Since plastics are flammable materials, it is desirable to impart fire retardancy or flame retardancy to molded articles made of plastics, such as resin sheets. In particular, flame retardant wallpaper for use as a building material, a fireproof poster for use in a shop, a shop sticker, a sheet member for use in a household appliance, a label for use in an automobile, a glass sticker for use in a railway vehicle, and the like are required to have a high level of flame retardancy (e.g., DIN4120, FMVSS-302, and the like).

As a material useful for a molded article made of the plastic, a propylene-based resin is known. However, in order to achieve high flame retardancy in a resin composition containing a propylene resin, it is necessary to blend a halogen-based flame retardant, a relatively large amount of an inorganic flame retardant, and the like.

Patent documents 1 and 2 describe propylene resin compositions containing a specific NOR HALS compound (NOR hindered amine light stabilizer) and a specific phosphorus compound as flame-retardant resin compositions without containing a halogen flame retardant or an inorganic flame retardant.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2015-510023

Patent document 2: japanese patent laid-open publication No. 2017-066299

Disclosure of Invention

Problems to be solved by the invention

However, the propylene resin compositions described in patent documents 1 and 2 have a problem in heat resistance, and the quality of the resulting molded articles is not sufficiently satisfactory. Further, from the viewpoint of safety of molded articles, higher flame retardancy has been demanded in recent years.

Further, it is known that phosphorus compounds and the like used as flame retardants often increase the surface tackiness of the obtained molded articles. If the surface of the molded article has a high viscosity, problems such as poor release from the mold and dirt adhering to the roller are induced during molding, and the moldability, i.e., moldability during molding is significantly deteriorated.

Therefore, a resin composition having both excellent heat resistance and flame retardancy and excellent moldability is required.

Accordingly, an object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a resin composition having both excellent heat resistance and flame retardancy and excellent moldability.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a resin composition containing a propylene-based resin and/or a vinyl-based resin, a NOR-based HALS compound having a specific structure, and a phosphorus-based compound having a specific flash point, and the content of the phosphorus-based compound is set to a predetermined range, and have completed the present invention.

That is, the present invention provides various specific embodiments shown below.

[1] A resin composition characterized by comprising:

a propylene-based resin and/or an ethylene-based resin,

a NOR-type HALS compound represented by the following formula (1) or the following formula (2), and

a phosphorus compound having a flash point of 360 ℃ or higher.

[ chemical formula 1]

[ chemical formula 2]

(in the formula (2), R is a group represented by the following formula (2-1))

[ chemical formula 3]

[2] The resin composition according to [1], wherein the phosphorus compound is contained in an amount of 0.1 to 7 parts by mass per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin.

[3] The resin composition according to [1] or [2], wherein the NOR-type HALS compound is contained in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin.

[4] The resin composition according to any one of [1] to [3], wherein the degree of hydrolysis of the phosphorus-based compound is 10% by mass or less.

[5] The resin composition according to any one of [1] to [4], wherein the ratio of the content of the phosphorus-based compound to the content of the NOR-type HALS compound is 0.5 to 30 on a mass basis.

[6] The resin composition according to any one of [1] to [5], wherein the phosphorus-based compound contains a phosphite compound and/or a phosphate compound.

[7] The resin composition according to any one of [1] to [6], wherein the resin composition contains an inorganic filler.

[8] The resin composition according to any one of [1] to [7], wherein the resin composition contains at least a propylene-based resin.

[9] A resin sheet comprising a layer formed using the resin composition according to any one of [1] to [8 ].

Effects of the invention

According to the present invention, a resin composition having both excellent heat resistance and flame retardancy and excellent moldability can be provided.

Detailed Description

The present invention will be described in detail below. The following description of the constituent elements is illustrative for describing the present invention, and the present invention is not limited to these contents. In the present specification, a numerical range expressed by "to" means a range including numerical values described before and after "to" as a lower limit value and an upper limit value.

[ resin composition ]

The resin composition of the present invention comprises a propylene resin and/or a vinyl resin, a NOR-type HALS compound represented by the following formula (1) or the following formula (2), and a phosphorus compound having a flash point of 360 ℃ or higher.

[ chemical formula 4]

[ chemical formula 5]

(in the formula (2), R is a group represented by the following formula (2-1))

[ chemical formula 6]

The resin composition of the above specific composition is less likely to change in color tone and flowability of the resin even when stored at a high temperature for a predetermined period of time. That is, the resin composition of the present invention is excellent in heat resistance. Further, a resin sheet having excellent flame retardancy can be obtained using the resin composition. Further, the obtained resin sheet had no tackiness on the surface and was excellent in moldability.

Hereinafter, the raw materials that can be used for the resin composition of the present invention will be described in detail.

< propylene resin >

Propylene-based resins are used as a main material of resin compositions, and impart film formability, water resistance, durability, lightweight properties, physical strength, and light transmittance to resin sheets formed using the resin compositions.

The propylene-based resin is not particularly limited as long as propylene is used as a main monomer. Examples of the propylene-based resin include isotactic polymers and syndiotactic polymers obtained by homopolymerizing propylene. In addition, a copolymer of propylene and an α -olefin such as ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, or the like, that is, a propylene- α -olefin copolymer, or the like, may be used as the main component. The copolymer may be a 2-membered or 3-or more-membered copolymer as the monomer component, or a random or block copolymer. In addition, a propylene homopolymer and a propylene copolymer may be used in combination. Among these, propylene homopolymer is preferable because it is easy to handle as a main raw material of the resin sheet.

As the propylene-based resin, various conventionally known propylene-based resins can be used. The MFR (Melt Flow Rate) of the propylene-based resin is, without any limitation, usually 0.5g/10 min or more, preferably 1.0g/10 min or more, usually 30g/10 min or less, and preferably 20g/10 min or less.

Since a propylene resin is less likely to thermally shrink than a later-described ethylene resin, a resin composition or a resin sheet using a propylene resin as a main material is less likely to cause dimensional deviation, and is excellent in processability and moldability. Therefore, as a main material of the resin composition used for the resin sheet, a propylene-based resin is more preferably used.

< ethylene resin >

The ethylene resin is used as a main material of the resin composition, similarly to the propylene resin, and imparts film formability, water resistance, durability, lightweight property, physical strength, and light transmittance to a resin sheet formed using the resin composition.

The vinyl resin is not particularly limited as long as ethylene is used as a main monomer.

The ethylene resin has a density of 0.940 to 0.965g/cm³The high-density polyethylene has a density of 0.920-0.935 g/cm³The medium density polyethylene has a density of 0.900-0.920 g/cm³Crystalline ethylene resins such as low-density polyethylene, and the like. In addition, a copolymer of ethylene and an α -olefin such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, or the like, that is, an ethylene- α -olefin copolymer, may be used as the main component. In addition, as the vinyl resin, an ethylene-vinyl acetate copolymer, an ethylene-cyclic olefin copolymer, or the like can be used. Among them, low-density polyethylene is preferable, and copolymers with α -olefins such as ethylene-butene copolymers and ethylene-octene copolymers are more preferable.

As a main material of the resin composition used for the resin sheet, a blend of a propylene-based resin and a vinyl-based resin can be used. As the propylene-based resin and the ethylene-based resin used as the blend, for example, any resin selected from the propylene-based resins and the ethylene-based resins exemplified above can be used.

< NOR type HALS compound >

The resin composition of the present invention contains a NOR-based HALS compound having a specific structure, and thus can inhibit deterioration of a propylene-based resin and/or a vinyl-based resin due to ultraviolet rays or the like, and can impart excellent weather resistance. Further, a resin composition and a resin sheet can be obtained which are suppressed in deterioration of a propylene resin and/or a ethylene resin in a high-temperature environment and which are excellent in heat resistance.

The NOR-type HALS compound is represented by the following formula (1) or the following formula (2).

[ chemical formula 7]

[ chemical formula 8]

(in the formula (2), R is a group represented by the following formula (2-1))

[ chemical formula 9]

The NOR-based HALS compound represented by the formula (1) or (2) functions as an excellent radical scavenger and acts to stop a combustion reaction when a resin composition or a resin sheet containing the NOR-based HALS compound burns. That is, excellent flame retardancy can be imparted to the resin composition and the resin sheet.

In particular, the NOR-based HALS compound represented by the formula (1) is more stable than the NOR-based HALS compound represented by the formula (2) by itself, and therefore, the coloring of the resin composition or the resin sheet can be further prevented. Further, the NOR-based HALS compound represented by the formula (1) has better compatibility with a propylene-based resin and/or an ethylene-based resin and is less likely to bleed out than the NOR-based HALS compound represented by the formula (2), and thus is more excellent in moldability.

Further, since the NOR-based HALS compound represented by the formula (1) is liquid at ordinary temperature, it is easily dispersed in a resin composition uniformly and finely when melt-kneaded with a propylene-based resin and/or an ethylene-based resin, and exhibits excellent heat resistance and flame retardancy.

In the resin composition of the present invention, the content of the NOR-based HALS compound represented by the formula (1) or the formula (2) is preferably 0.1 part by mass or more, more preferably 0.22 part by mass or more, further preferably 0.5 part by mass or more, further preferably 0.6 part by mass or more, and particularly preferably 0.7 part by mass or more, per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin. The content is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, further preferably 1.5 parts by mass or less, and particularly preferably 1.15 parts by mass or less, per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin. When the content of the NOR-based HALS compound represented by the formula (1) or the formula (2) is not less than the lower limit, the heat resistance of the resin composition is improved and the flame retardancy of the resin sheet is improved. If the content of the NOR-type HALS compound represented by the formula (1) or the formula (2) is not more than the upper limit, the influence of the NOR-type HALS compound itself being burned can be reduced and the decrease in the flame retardant effect of the resin composition or the resin sheet can be suppressed before the combustion suppressing effect by the trapping of radicals possessed by the NOR-type HALS compound is exhibited. Further, the deterioration of moldability and printability due to bleeding of the NOR-type HALS compound can be suppressed. Furthermore, the amount of the NOR-type HALS compound used can be suppressed to be high at a high cost, and the economic efficiency is excellent. The NOR-type HALS compound represented by the formula (1) or the formula (2) may be used alone or in combination of 2 kinds.

< phosphorus-based Compound having flash Point of 360 ℃ or higher >

The phosphorus-based compound serves as a flame retardant, and when the propylene-based resin and/or the ethylene-based resin is burned, the combustion component is carbonized (carbonized) and cured to form an air-barrier coating film, thereby exhibiting an action of stopping the combustion reaction, an action as a radical scavenger similar to the NOR-based HALS compound, and an action of diluting the oxygen concentration generated by phosphine gas (phosphine gas) generated during decomposition of the phosphorus-based flame retardant. By using the phosphorus-based compound and the NOR-type HALS compound represented by the formula (1) or the formula (2) in combination in a predetermined amount, excellent flame retardancy can be imparted to the resin composition and the resin sheet.

The phosphorus-based compound used in the present invention has a flash point of 360 ℃ or higher, preferably a flash point of 400 ℃ or higher, and more preferably 430 ℃ or higher. If the flash point of the phosphorus-based compound is not lower than the lower limit, the resin composition or the resin sheet can be provided with higher flame retardancy.

The flash point of the propylene-based resin and/or the ethylene-based resin is generally considered to be 300 to 450 ℃. However, it is considered that the thermal decomposition starts from about 250 ℃, and a decomposition product generated by the thermal decomposition causes ignition. It is presumed that when a phosphorus compound having a flash point of about the same temperature as or lower than the thermal decomposition initiation temperature of the propylene-based resin and/or the ethylene-based resin is mixed, the phosphorus compound itself may burn before the flame retardant effect is exerted, and the flame retardancy of the resin composition or the resin sheet cannot be sufficiently improved. From the above-described viewpoints, it is considered that a good flame retardancy can be imparted by using, as a flame retardant, a phosphorus-based compound having a flash point higher than the thermal decomposition initiation temperature of the propylene-based resin and/or the ethylene-based resin, specifically, a flash point of 360 ℃.

The degree of hydrolysis of the phosphorus-based compound is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass or less. Since the molecules become finer if the phosphorus-based compound is hydrolyzed, the hydrolyzed phosphorus-based compound is likely to move in the resin, and the hydrolyzed phosphorus-based compound is likely to bleed out when stretched, heated, or irradiated with light. If the degree of hydrolysis of the phosphorus-based compound is not more than the upper limit, the decrease in flame retardant effect, and the decrease in moldability and printability due to bleeding can be suppressed.

The phosphorus-based compound used in the present invention is not particularly limited as long as it has a flash point of 360 ℃ or higher, and examples thereof include a phosphorous acid compound, a phosphoric acid compound, a phosphite ester compound, and a phosphate ester compound. Among these, phosphite compounds and phosphate compounds are preferable, and phosphite compounds are more preferable from the viewpoint of excellent effect of suppressing the exudation of phosphorus-based compounds.

The phosphite compound is preferably a phosphite compound represented by the formula (3) described later.

In the phosphite ester compound represented by the following formula (3), R⁴And R⁵May be the same or different and represents a substituted or unsubstituted C_1～30Alkyl, substituted or unsubstituted C_3～30Cycloalkyl, substituted or unsubstituted C_6～30And (4) an aryl group.

[ chemical formula 10]

Wherein R is⁴And R⁵Each independently preferably being substituted or unsubstituted C_6～30Aryl, more preferably substituted or unsubstituted C_6～15Aryl, particularly preferably C having a substituent_6～15And (4) an aryl group.

At R⁴And R⁵Is C having a substituent_6～15In the case of an aryl group, the phosphite compound represented by formula (3) is preferably a compound represented by formula (4) below.

[ chemical formula 11]

In the formula (4), R⁶、R⁷、R⁹、R¹⁰、R¹²、R¹³、R¹⁵And R¹⁶Each independently represents a hydrogen atom or C_1～5Alkyl radical, R⁸、R¹¹、R¹⁴And R¹⁷Each independently represents C_1～5Alkyl radical, C_6～15Aryl or aralkyl. Aralkyl is C_1～51 hydrogen atom of the alkyl radical being bound by C_6～15Aryl substituted substituents. And b 1-b 4 each independently represent an integer of 0-3. R⁶、R⁷、R⁹、R¹⁰、R¹²、R¹³、R¹⁵And R¹⁶Preferably methyl, and b1 to b4 preferably represent 0.

Specific examples of the phosphite compound represented by formula (3) or (4) include bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.

The degree of hydrolysis [ mass% ] of the phosphorus-based compound refers to the mass increase rate of the phosphorus-based compound after 5g of the phosphorus-based compound is allowed to stand for 400 hours under the humidification and heating conditions with a relative humidity of 95% to 50 ℃. This value is an index of the degree of hydrolysis of the phosphorus-based compound, and a larger value indicates a higher degree of hydrolysis.

If the phosphorus-based compound is hydrolyzed, the flame retardant effect may be reduced, and moldability and printability due to bleeding may be reduced, so that the value of the degree of hydrolysis of the phosphorus-based compound is preferably small.

The phosphorus-based compounds may be used alone or in combination of 2 or more.

The content of the phosphorus-containing compound in the resin composition of the present invention is preferably 0.1 part by mass or more, more preferably 0.25 part by mass or more, further preferably 0.5 part by mass or more, further preferably 0.8 part by mass or more, and particularly preferably 1.5 parts by mass or more, per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin. The content is preferably 7 parts by mass or less, more preferably 6 parts by mass or less, further preferably 5.8 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less, per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin.

When the content of the phosphorus-based compound is not less than the lower limit, the heat resistance of the resin composition and the flame retardancy of the resin sheet can be effectively improved by using the compound in combination with the NOR-type HALS compound. Further, if the content of the phosphorus compound is not more than the upper limit, the bleeding of the phosphorus compound in the resin sheet can be further reduced, and therefore, the adhesiveness of the resin sheet can be suppressed and the moldability is excellent.

That is, when the content of the phosphorus compound is set to a predetermined range, the resin composition has an excellent balance among heat resistance, flame retardancy of the resin sheet, and moldability due to the bleeding-out suppressing effect of the phosphorus compound.

The resin composition of the present invention may contain a phosphorus compound having a flash point of less than 360 ℃ in a range that does not inhibit the effects of heat resistance, flame retardancy, moldability, and the like.

< content ratio of NOR-type HALS compound to phosphorus-based compound >

In the resin composition of the present invention, the ratio of the content of the phosphorus-based compound to the content of the NOR-based HALS compound [ (content of the phosphorus-based compound)/(content of the NOR-based HALS compound) ] is preferably 0.5 or more, more preferably 0.9 or more, still more preferably 1.0 or more, still more preferably 1.1 or more, and particularly preferably 1.2 or more on a mass basis. The ratio of the content is preferably 30 or less, more preferably 20 or less, further preferably 14 or less, further preferably 6 or less, and particularly preferably 4 or less on a mass basis. Namely, there is a tendency that: the content of the phosphorus-based compound is preferably relatively large relative to the content of the NOR-type HALS compound. If the ratio of the content of the phosphorus-based compound to the content of the NOR-type HALS compound is within the above range, the flame retardancy is particularly improved. If the ratio of the content of the phosphorus-based compound to the content of the NOR-type HALS compound is not less than the lower limit, the resin composition or the resin sheet can be provided with higher flame retardancy. Further, if the content is less than the upper limit, the effect according to the amount to be blended can be obtained, and therefore, the composition is economical, and also the bleeding of the phosphorus-based compound can be suppressed, and the moldability is excellent, so that it is preferable.

< inorganic Filler >

The resin composition of the present invention may contain an inorganic filler within a range that does not inhibit the effects of heat resistance, flame retardancy, and the like. The inorganic filler is also referred to as inorganic fine powder.

By containing the inorganic filler, the whiteness or opacity of the resulting resin sheet can be improved. Further, the inorganic filler acts as a void nucleating material when the resin sheet is stretch-molded, and therefore, the resin sheet can be made porous.

Therefore, the resin composition containing the inorganic filler is useful as a raw material of so-called synthetic paper.

On the other hand, if the inorganic filler is blended, the surface area of the resin composition or resin sheet increases, and therefore, when the resin composition or resin sheet burns, the combustion reaction may be accelerated. This is because, when a resin composition or a resin sheet is ignited, the inorganic filler melts the surrounding propylene-based resin and/or ethylene-based resin due to its high thermal conductivity, and further acts to promote burning as in the case of a candle wick.

The inventors of the present invention found that: when the content of the inorganic filler (particularly, calcium carbonate) is about 30 parts by mass with respect to 100 parts by mass of the propylene-based resin and/or the ethylene-based resin, desired heat resistance, flame retardancy, and the like can be easily maintained. Therefore, it is found that a resin sheet excellent in heat resistance and flame retardancy can be easily obtained from a resin composition containing an inorganic filler.

From the above viewpoint, the content of the inorganic filler is preferably 1 part by mass or more, more preferably 5 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less, per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin. When the content of the inorganic filler is not less than the lower limit, the whiteness and opacity of the resin sheet are easily improved, and the resin sheet is easily made porous. Further, if the content of the inorganic filler is not more than the above upper limit, the decrease in flame retardancy is easily suppressed.

Specific examples of the inorganic filler include fine powders such as ground calcium carbonate, light calcium carbonate, calcined clay, talc, zeolite, titanium oxide, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, and silica, and hollow glass beads. Among them, heavy calcium carbonate and light calcium carbonate are commercially available in various forms, and are preferable because desired average particle diameter and particle size distribution are easily obtained, and optical properties such as whiteness and opacity of the resin sheet are easily designed. These can be used alone in 1 or a combination of 2 or more.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.2 μm or more, preferably 10 μm or less, and more preferably 5 μm or less. When the average particle diameter of the inorganic filler is not less than the lower limit, the whiteness and opacity of the resin sheet are easily improved, and the resin sheet is easily made porous. If the amount is less than the upper limit, the resin sheet is easily prevented from being broken during stretching due to the incorporation of coarse particles.

The average particle diameter of the inorganic filler is an average value calculated based on 100 particle diameters of the inorganic filler randomly extracted from an observation area measured by observing a cross section of the resin sheet in the thickness direction with an electron microscope. The particle diameter of the inorganic filler in this case is determined by the maximum value (maximum diameter) of the distance between 2 points on the outline of the particle.

< other additives >

The resin composition may contain known additives such as a dispersant, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, an anti-blocking agent, a crystal nucleating agent, and a lubricant, if necessary. Further, a light stabilizer other than the NOR type HALS compound or a phosphorus compound having a flash point of less than 360 ℃ may be blended in the range not to inhibit the effect of the present invention.

The dispersant is used, for example, to highly disperse the inorganic filler in the resin composition. Examples of the dispersant include a silane coupling agent, higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acid, polymethacrylic acid, maleic anhydride-modified polypropylene, and salts thereof.

The content of the dispersant is not particularly limited, and is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin, for example, depending on the content of the inorganic filler. When the content of the dispersant is 0.01 part by mass or more, the inorganic filler is likely to be uniformly and finely dispersed in the propylene resin and/or the ethylene resin, and the decrease in flame retardancy tends to be easily suppressed. Further, if the content of the dispersant is 5 parts by mass or less, it is easy to prevent the viscosity and light transmittance from being inhibited by the remaining dispersant.

The resin composition of the present invention may contain a thermoplastic resin other than a propylene-based resin and/or an ethylene-based resin, within a range not to impair the effects of the present invention. Examples of the thermoplastic resin include a crystalline olefin resin other than ethylene or propylene, such as polymethyl-1-pentene, an amide resin, such as nylon-6, nylon-66, nylon-610, and nylon-612, a thermoplastic polyester, such as polyethylene terephthalate or a copolymer thereof, polyethylene naphthalate, and an aliphatic polyester, and a thermoplastic resin, such as polycarbonate, atactic polystyrene, syndiotactic polystyrene, and polyphenylene sulfide. These may be used in combination of 2 or more. Among them, crystalline olefin resins other than ethylene-based or propylene-based resins are preferable.

The content of the thermoplastic resin in the resin composition of the present invention is usually 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the propylene-based resin and/or the ethylene-based resin, as long as the effect of the present invention is not hindered.

[ resin sheet ]

The resin sheet of the present invention includes a layer formed using the resin composition.

The resin sheet may have a single-layer structure or a multilayer structure as long as it includes the above-described layer.

When the resin sheet has a multilayer structure, the resin compositions constituting the respective layers may be the same or different. When the resin sheet has a multilayer structure and the resin compositions constituting the respective layers are different from each other, at least one layer may be formed using the resin composition of the present invention, and when the resin sheet includes a plurality of layers formed using the resin composition of the present invention, the resin compositions constituting the respective layers (i.e., the kind or content of the compound included in the layers) may be the same or different from each other. For example, if the content of the phosphorus-based compound in the outermost layer is large, the flame retardancy of the resin sheet is easily improved, and if the content of the inorganic filler is large, the appearance of the synthetic paper is easily realized.

The resin sheet of the present invention may be an unstretched sheet or a stretched sheet. In the case of a stretched sheet, the number of stretching axes may be one direction or two or more directions.

The thickness of the resin sheet of the present invention is not particularly limited as long as it is appropriately set according to the desired performance, and is preferably 30 μm or more, more preferably 40 μm or more, and still more preferably 50 μm or more. The thickness of the resin sheet is preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 200 μm or less. If the thickness of the resin sheet is not less than the lower limit, the resin sheet has sufficient mechanical strength, and the resin sheet is easily prevented from being broken during stretch molding or use. Further, if the thickness of the resin sheet is not more than the upper limit, the resin sheet tends not to be excessively heavy and handling becomes easy.

The thickness of the resin sheet is measured in accordance with JIS K7130: 1999 the obtained value was measured. When the resin sheet has a multilayer structure, the value is measured as a whole of a plurality of layers. When the resin sheet has a multilayer structure, the thickness of each layer is observed with an electron microscope, and the interface between the layers is judged from the appearance, and the thickness ratio is determined, and the product of the thickness of the entire resin sheet and the thickness ratio of each layer obtained by the above measurement is calculated.

[ Properties of resin composition and resin sheet ]

< color difference Δ E >

The color difference Δ E is an index value representing a change in the color tone of the resin composition at high temperature. The color difference Δ E represents the thermal stability of the resin composition, and a low value means that the resin composition is less colored at high temperatures. The color difference Δ E in the present invention is a value measured under the conditions described in the examples described below.

Specifically, first, a sample in which pellets of the resin composition were heated in an oven in which the temperature of the atmosphere was set to 150 ℃ for 7 days and a sample in which the pellets were stored at normal temperature for the same period of time were prepared. Next, about 5g of each pellet sample was hydraulically pressed at 230 ℃ using a compression molding machine to obtain a disk-shaped resin sheet for evaluation having a diameter of about 50mm and a thickness of about 2 mm. The obtained evaluation resin sheet was measured for brightness L, color coordinates a, b before and after heating using a colorimeter, and color difference Δ E ab in a system denoted by L a b was calculated as color difference Δ E.

The color difference Δ E of the resin composition of the present invention is preferably 15 or less, more preferably 10 or less, from the viewpoint of reducing coloring. The color difference Δ E of the resin composition tends to be kept low by decreasing the content of the phosphorus-based compound, but the color difference Δ E of the resin composition is usually 0.5 or more by blending an amount necessary for securing flame retardancy.

< Density >

The density of the resin sheet of the present invention is preferably 0.5g/cm from the viewpoint of maintaining the strength of the resin sheet³Above, more preferably 0.6g/cm³The above. On the other hand, the density of the resin sheet is preferably 1.3g/cm from the viewpoint of weight reduction of the resin sheet³Hereinafter, more preferably 1.0g/cm³The following.

The density of the resin sheet of the present invention can be determined according to JIS K7112: 1999, the method was calculated from the following equation based on the thickness of the resin sheet and the weight of the sample punched out to a size of 10cm × 10 cm.

ρ＝Wf/Tf

Wherein ρ, Wf and Tf are as follows.

ρ: density (g/cm) of resin sheet³)

Wf: weight per unit area (g/cm) of resin sheet²)

Tf: thickness (cm) of resin sheet

< porosity >

The porosity of the resin sheet of the present invention is preferably 1% or more, more preferably 10% or more, from the viewpoint of opacity or weight reduction. On the other hand, the void ratio of the resin sheet is preferably 60% or less, more preferably 50% or less, from the viewpoint of maintaining the mechanical strength and flame retardant performance.

The porosity of the resin sheet can be determined from the ratio of the area occupied by the pores in a predetermined region of the cross section of the resin sheet observed with an electron microscope. Specifically, an arbitrary part of the resin sheet to be measured is cut out, embedded in an epoxy resin and cured, and then cut perpendicularly in the direction of the surface of the film to be measured with a microtome, and attached to the observation sample stage so that the cut surface becomes the observation surface. The observation surface is subjected to vapor deposition of gold, gold-palladium, or the like, the pores of the resin sheet are observed at an arbitrary magnification (for example, a magnification of 500 to 3000 times) that is easy to observe with an electron microscope, and the observed region is read as image data. The image data obtained is subjected to image processing by an image analyzer to obtain the area ratio (%) of the void portion in a predetermined area of the resin sheet as a void ratio (%). In this case, the porosity can be determined by averaging the measured values of any 10 or more observations.

[ method for producing resin composition and resin sheet ]

The resin composition of the present invention can be produced by a conventionally known method. Generally, the respective components are thoroughly mixed and then melt-kneaded by a single-screw or twin-screw extruder. The components were not mixed in advance, or only a part thereof was mixed in advance, and the mixture was fed to an extruder using a feeder and melt-kneaded to prepare a resin composition. Further, a master batch may be prepared by melt-kneading a mixture of a propylene-based resin and/or an ethylene-based resin and a part of other components, and then the remaining propylene-based resin and/or ethylene-based resin and other components may be melt-kneaded. When the resin sheet has a multilayer structure, the resin composition for forming each layer may be prepared so as to correspond to each layer. The heating temperature during melt kneading is usually about 180 to 300 ℃ for the rolls of the extruder, particularly about 200 to 250 ℃ for the rolls in the compression zone, and usually about 200 to 250 ℃ for the resin to be ejected.

Next, the obtained resin composition is melt-extruded into a sheet shape, and can be molded into a resin sheet. Then, the obtained resin sheet is stretched in at least one direction as needed. Further, if necessary, the resin sheet may be obtained by performing annealing (heat treatment) and then slitting the ear portions.

Various conventionally known methods can be used for producing the resin sheet of the present invention. For example, when the resin sheet has a single-layer structure, the resin composition containing the above components may be melt-kneaded, extruded from a single die, and stretched as needed. In the case of a resin sheet having a multilayer structure, a multilayer resin sheet having a plurality of resin sheets stacked thereon can be produced by a coextrusion method using a multilayer die using a feed block or a manifold, an extrusion lamination method using a plurality of dies, or the like. Further, the resin sheet can also be produced by a method combining a coextrusion method and an extrusion lamination method using a multilayer die.

The stretching of the resin sheet can be performed by various known methods. Specific examples thereof include a longitudinal stretching method using a difference in peripheral speed between roll groups, a transverse stretching method using a tenter oven, a sequential biaxial stretching method in which the longitudinal stretching and the transverse stretching are performed in a forward or reverse order, a rolling method, a simultaneous biaxial stretching method using a combination of a tenter oven and a linear motor, and a simultaneous biaxial stretching method using a combination of a tenter oven and a pantograph. Further, a simultaneous biaxial stretching method using a tube method, which is a stretching method of an inflation film, may be mentioned.

The temperature at the time of stretching is not particularly limited, and may be carried out in a temperature range suitable for stretching the propylene-based resin and/or the ethylene-based resin. Specifically, it is preferably carried out at a temperature 2 to 15 ℃ or higher lower than the melting point of the propylene-based resin and/or the ethylene-based resin. For example, when the resin composition of the present invention contains an inorganic filler, a stretched resin sheet having voids with a core of the inorganic filler or the like enclosed therein can be obtained by stretching the resin composition at a temperature lower than the melting point of the propylene-based resin and/or the ethylene-based resin. In this case, the resin sheet has appropriate opacity and light weight. The stretching may be performed at a temperature not lower than the glass transition point of the propylene-based resin and/or the ethylene-based resin used mainly (most used in terms of mass ratio) in the resin sheet and 1 to 70 ℃ lower than the melting point of the crystalline portion of the propylene-based resin and/or the ethylene-based resin, or may be performed at a temperature 1 ℃ lower than the melting point and 2 ℃ higher than the melting point.

The stretch ratio of the resin sheet is not particularly limited, and may be determined as appropriate in consideration of the properties of the resin sheet to be obtained. The stretching ratio in the longitudinal uniaxial stretching is preferably in the range of 2 to 8 times, more preferably in the range of 3 to 7 times, and further preferably in the range of 4 to 6 times. The stretching ratio in the transverse uniaxial stretching is preferably in the range of 2 to 12 times, more preferably in the range of 4 to 10 times, and still more preferably in the range of 6 to 9 times. In the case of biaxial stretching, the area stretching magnification (product of longitudinal magnification and transverse magnification) is preferably in the range of 4 to 70 times, more preferably in the range of 10 to 60 times, and still more preferably in the range of 20 to 50 times.

When the resin sheets have a multilayer structure, the number of stretching axes and the stretching ratio of the resin sheets constituting each layer may be the same or different.

Hereinafter, a preferred method for producing a resin sheet having a single-layer structure will be described.

First, the resin composition is melt-kneaded using an extruder, supplied to a single die, extruded into a sheet, and cooled to a temperature lower than the melting point of the propylene-based resin and/or the ethylene-based resin, for example, to 40 to 85 ℃. Then, the unstretched resin sheet is stretched 3 to 10 times in the longitudinal direction at a stretching temperature 2 to 15 ℃ or higher lower than the melting point of the propylene resin and/or the ethylene resin. Thus, a uniaxially stretched resin sheet oriented in the longitudinal direction was obtained. Then, the uniaxially stretched resin sheet is stretched 4 to 12 times in the transverse direction at a stretching temperature 2 to 15 ℃ lower than the melting point of the propylene resin and/or the ethylene resin. Thus, a biaxially stretched resin sheet was obtained.

< Heat treatment >

The stretched resin sheet is preferably subjected to a heat treatment. The heat treatment is preferably carried out at a temperature higher than the melting point of the propylene resin and/or the ethylene resin by 1 to 15 ℃. By performing the heat treatment, crystallization of the amorphous portion of the propylene-based resin and/or the ethylene-based resin is promoted, so that the heat shrinkage rate in the stretching direction is reduced, and the dimensional change of the resin sheet is reduced. The method of heat treatment is typically carried out in a roll-heated or heated oven, although combinations thereof are also possible.

< surface treatment >

The stretched resin sheet may be subjected to a surface treatment. By performing the surface treatment, the secondary processability of the resin sheet can be improved. Examples of the surface treatment include oxidation treatments such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, and ozone treatment. Further, the stretched resin sheet may be subjected to oxidation treatment and then coated with an anchor agent and an antistatic agent.

[ use of resin sheet ]

The use of the resin sheet of the present invention is not particularly limited, and the resin sheet is particularly preferably used for applications such as printing paper, label paper, and a reflective sheet.

Examples of applications for printing include flame-retardant wallpaper used as a building material, a fire poster used in a store, a lighting poster, a point of sale advertisement (POP), and the like. Examples of the application of the label or the seal include a shop sticker used in a shop, a label or a wire harness used in an automobile or the like, and a glass sticker used in a railway vehicle or the like. Examples of applications requiring a light reflection function include a light reflection sheet for a liquid crystal display, a light reflection sheet for a decorative signboard, a light reflection sheet for indoor lighting, an agricultural multilayer sheet, a reflector for photography, and a back cover of a copying machine.

Hereinafter, the resin sheet for printing will be described in detail. Although the resin sheet can be directly printed, an ink receiving layer is preferably disposed as a printed layer on at least one surface of the resin sheet.

(ink-receiving layer)

The ink-receiving layer exhibits an effect of improving the printability of the resin sheet, particularly the ink transferability and the ink adhesion.

The ink-receiving layer preferably contains at least 1 of a binder and an antistatic agent. The ink-receiving layer preferably further contains a crosslinking agent. In addition, the ink-receiving layer may contain an anti-blocking agent, a colorant, an antifoaming agent, a mildewproofing agent, a lubricant, and the like as necessary.

Adhesive

The adhesive is not particularly limited as long as it has adhesiveness and can be applied to the surface of the resin sheet.

Examples of the binder include ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer and metal salts thereof (Zn, Al, Li, K, Na, etc.), ethylene- (meth) acrylic acid (C)_1-8) Ethylene copolymers such as alkyl ester copolymers; modification with maleic acidAcid-modified polyolefins such as polyethylene, maleic acid-modified polypropylene, and maleic acid-modified ethylene-vinyl acetate copolymer; monohydroxy group (C)_3-6) Hydroxyl-modified polyolefins such as alkyl-modified polyethylene; chlorinated polyolefins; polyurethanes such as polyester polyurethane and polycarbonate polyurethane; polyethyleneimine such as polyethyleneimine and poly (ethyleneimine-urea), and modified products thereof; modified polyamine polyamides such as ethyleneimine adducts of polyamine polyamides, and various (alkyl, cycloalkyl, allyl, aralkyl, benzyl, cyclopentyl) modified products of polyamine polyamides.

In the case of particularly imparting water resistance to the ink-receiving layer, a water-dispersible (emulsion) binder may be selected.

The content ratio of the binder in the ink-receiving layer is not particularly limited, and is usually 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, usually 100% by mass or less, and preferably 99.5% by mass or less, based on the total mass of the ink-receiving layer.

Antistatic agent

Examples of the antistatic agent include low molecular weight organic compounds, conductive inorganic compounds, so-called electron conductive polymers, nonionic polymer type antistatic agents, quaternary ammonium salt type copolymers, alkali metal salt containing polymers, and the like. Specific examples thereof include low molecular weight organic compounds such as stearic acid monoglyceride, alkyl diethanol amine, sorbitan monolaurate, alkylbenzene sulfonate, and alkyl diphenyl ether sulfonate; conductive inorganic compounds such as ITO (indium-doped tin oxide), ATO (antimony-doped tin oxide), and graphite whiskers; so-called electron conductive polymers that exhibit conductivity by pi electrons in molecular chains such as polythiophene, polypyrrole (ポリピーロイル), and polyaniline; nonionic polymer-type antistatic agents such as polyethylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene diamine; quaternary ammonium salt type copolymers such as polyvinyl benzyl trimethyl ammonium chloride and polydimethylaminoethyl methacrylate quaternary ammonium salt; and polymers containing alkali metal salts such as alkali metal ion additives to polymers containing oxyalkylene groups or hydroxyl groups.

The surface resistivity of the resin sheet to which the antistatic agent is applied is preferablyIs 1 × 10²～1×10¹³Omega, more preferably 1 × 10⁶～1×10¹²Ω。

The content ratio of the antistatic agent contained in the ink-receiving layer is not particularly limited, and is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, usually 50% by mass or less, and preferably 40% by mass or less, relative to the total mass of the ink-receiving layer.

Crosslinking agent

The crosslinking agent reacts with the adhesive or the antistatic agent, or the adhesive or the antistatic agent is enclosed in the mesh network formed by the crosslinking agent, whereby the adhesive or the antistatic agent is fixed to the surface of the resin sheet. As a result, for example, the adhesion and water resistance of the printing performed on the resin sheet are improved.

Examples of the crosslinking agent include those having 2 or more functions as a reactive functional group such as a hydroxyl group (hydroxy) group, a carboxyl group, an epoxy group, an isocyanate group, an aldehyde group, an oxazoline skeleton, and a carbodiimide skeleton. Among them, bisphenol a-epichlorohydrin resins, epichlorohydrin resins of polyamine polyamides, aliphatic epoxy resins, epoxy novolac resins, alicyclic epoxy resins, brominated epoxy resins, and the like are preferable, and epichlorohydrin adducts, monofunctional or polyfunctional glycidyl ethers or glycidyl esters of polyamine polyamides are more preferable.

The content ratio of the crosslinking agent contained in the ink-receiving layer is not particularly limited, and is usually 15 mass% or more, preferably 20 mass% or more, usually 45 mass% or less, and preferably 40 mass% or less with respect to the total mass of the ink-receiving layer. When the content of the crosslinking agent is in the above range, the adhesion and water resistance of the printing ink can be improved.

(lamination of ink-receiving layer)

The ink-receiving layer is preferably formed by applying a coating liquid. From the viewpoint of ease of process control, the solvent used in the coating liquid may be water; water-soluble solvents such as methanol, ethanol, isopropanol, acetone, and methyl ethyl ketone; and water-insoluble solvents such as ethyl acetate, toluene, and xylene.

The coating liquid is preferably used in the form of a solution or dispersion in which the above components such as a binder are uniformly dissolved or dispersed in the above solvent. Among these, from the viewpoint of safety and odor, it is more preferable to use a coating solution in which all of the above components are water-soluble or water-dispersible components and an aqueous solution or aqueous dispersion is used.

From the viewpoint of reducing the drying load, the solid content concentration in the coating liquid is preferably 0.1 mass% or more, and more preferably 0.2 mass% or more. From the viewpoint of obtaining a uniform coating surface, the amount is preferably 20% by mass or less, and more preferably 10% by mass or less.

Examples of the coating method include a method using a coating apparatus such as a gravure coater, a microgravure coater, a reverse coater, a blade coater, a meyer bar coater, or an air knife coater.

When water or a water-soluble organic solvent is used as the solvent, it is preferable to perform activation treatment exemplified by corona discharge treatment on the surface of the resin sheet on which the coating liquid has been applied in advance, from the viewpoint of suppressing dishing of the coating liquid and uniformly applying the coating liquid. Further, it is also preferable to apply the coating liquid to the surface of the resin sheet in advance, and dry the coating layer to remove the solvent.

The ink-receiving layer is preferably 0.01 to 7g/m in terms of the amount of solid content applied to one side of the dried ink-receiving layer²More preferably 0.01 to 5g/m²Particularly preferably 0.05 to 3g/m². If the amount of the ink-receiving layer is in the above range, the ink transferability and adhesion are easily improved. If the amount of the ink-receiving layer to be applied is not more than the upper limit, the decrease in adhesion of the ink due to the aggregation breakdown in the ink-receiving layer can be easily suppressed. On the other hand, if the coating amount of the ink-receiving layer is not less than the lower limit, the ink transferability and adhesion are easily expressed.

< processing of resin sheet >

(printing and decoration)

The resin sheet of the present invention can be printed on the surface, and preferably, the surface provided with an ink-receiving layer is printed on the surface. Examples of the print information include a photographic image, a design, a bar code, a manufacturer, a sales company name, a character, a product name, and a usage method.

Examples of the printing method include gravure printing, offset printing, flexographic printing, seal printing, and screen printing.

In addition to printing, decoration such as transfer foil and hologram may be performed. Secure elements such as threads are also included in the decoration. Both printing and decoration may also be implemented.

Examples

The present invention will be specifically described below with reference to examples. Materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples may be appropriately changed without departing from the gist of the present invention. Therefore, the present invention is not limited to the following examples.

< example 1 >

92.8 parts by mass of a propylene homopolymer (trade name: NOVATEC PP FY6, manufactured by Japan Polypropylene Co., Ltd.), 1 part by mass of a NOR-type HALS compound (trade name: Adeka Stab LA-81, manufactured by ADEKA Co., Ltd.) having a Chemical structure represented by the formula (1), 1.2 parts by mass of a phosphorus-based compound (trade name: DOVERPHOS S S-9228, manufactured by Dover Chemical Co., Ltd.) having a flash point of 440 ℃ or higher, and 5 parts by mass of an inorganic filler (trade name: TIPAQUE CR-60, manufactured by Stone industries, Ltd.) were mixed by a super mixer to obtain a resin composition of example 1. The obtained resin composition was melt-kneaded in a twin-screw kneader set at 230 ℃, and the kneaded product was extruded from a die into a strand shape, cooled in a water tank, and cut with a pelletizer to obtain pellets.

Next, the obtained pellets were melt-kneaded again using an extruder set at 230 ℃, and the kneaded product was extruded from a T-die into a sheet shape, and cooled to 60 ℃ by a cooling device, to obtain a single-layer unstretched resin sheet.

Next, the unstretched resin sheet was heated to 143 ℃, then uniaxially stretched at a stretch ratio of 4.2 times in the conveying direction (longitudinal direction) of the resin sheet by an inter-roll stretching method using a difference in peripheral speed between a plurality of roll groups, and then cooled at 60 ℃, to obtain a uniaxially stretched resin sheet.

Next, the resin sheet obtained by the uniaxial stretching was reheated to 160 ℃ using a tenter oven, stretched at a stretch ratio of 8.5 times in the width direction (transverse direction) of the resin sheet by a clip stretching method using a tenter stretcher, and further annealed at 160 ℃ for 2 seconds in an oven while being held by clips. Then, the sheet was cooled to 60 ℃ and the ears were cut to obtain a single-layer resin sheet subjected to sequential biaxial stretching as the resin sheet of example 1. The thickness of the resin sheet of example 1 was 100 μm. The sheet was transported at a speed of 120 m/min.

Using the pellets of the resin composition of example 1 obtained above, heat resistance was evaluated as follows. Further, moldability and flame retardancy were evaluated as follows using the resin sheet of example 1. The results are summarized in Table 2.

< examples 2 to 9 and comparative examples 1 to 9 >

Resin compositions and resin sheets of examples 2 to 9 and comparative examples 1 to 9 were obtained by the same procedure as in example 1 except that the resin composition in example 1 was changed to the proportions shown in tables 2 and 3 using the raw materials shown in table 1.

The resin composition and the resin sheet thus obtained were used to perform the same evaluation. The results are summarized in tables 2 and 3.

In tables 2 and 3, the NOR-based HALS compound, the phosphorus-based compound, and the inorganic filler are abbreviated as those in table 1. The NOR type HALS compound, the phosphorus compound and the inorganic filler corresponding to the respective abbreviations are as follows. NH2 is a NOR-based HALS compound having a chemical structure represented by formula (2).

NH 1: bis (1-undecyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) carbonate (trade name: Adeka Stab LA-81, manufactured by ADEKA)

NH 2: reaction product of 2, 4-bis ((1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino) -6-chloro-s-triazine with N, N' -bis (3-aminopropyl) ethylenediamine (trade name: Flame Stab NOR-116FF, manufactured by BASF JAPAN Co., Ltd.)

PH 1: bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (trade name: DOVERPHOS S-9228, manufactured by Dover Chemical Co., Ltd.)

PH 2: compound having a main skeleton of an ester structure of pentaerythritol and 2 phosphoric acids (trade name: Fire Guard FCX-210, manufactured by Imperial corporation)

PH 3: reaction product of phenol, 4' - (propane-2, 2-diyl) diphenol and trichlorophosphine oxide (trade name: Adeka Stab FP-600, manufactured by ADEKA Co., Ltd.)

PH 4: tris (2, 4-di-tert-butylphenyl) phosphite (trade name: IRGAFOS 168, manufactured by BASF Japan)

TI: rutile type titanium dioxide Fine powder (trade name: TIPAQUE CR-60, product of Shidai industries, Ltd.)

CA: ground calcium carbonate Fine powder (trade name: SOFTON 1800, manufactured by Beibei Kogyou Kogyo Co., Ltd.)

[ evaluation method ]

The resin compositions and resin sheets obtained in the examples and comparative examples were subjected to physical property evaluations according to the following evaluation methods and evaluation criteria.

< thickness >

The thickness of the resin sheets obtained in the examples and comparative examples was measured using a constant pressure thickness measuring instrument (equipment name: PG-01J, manufactured by TECCLOCK corporation) in accordance with JIS K7130: 1999, found it.

< moldability >

The moldability of the resin sheets obtained in the examples and comparative examples was evaluated as follows.

If a large amount of bleeding occurs, stickiness occurs on the surface of the resin sheet, and thus various problems such as adhesion to a roller and blocking between sheets during storage after molding occur, and the production becomes difficult. Therefore, when stickiness occurred on the surface of the resin sheet, the evaluation was D.

In addition, even when the surface of the resin sheet is produced without adhesion, bleeding is generated to some extent. The oozing substance, i.e., the oozing liquid, is gradually transferred from the surface of the resin sheet to the roller, and the roller is contaminated. Since the roll needs to be cleaned depending on the degree of contamination, it is desirable to prevent the exudate from being transferred (adhered) to the roll as much as possible from the viewpoint of time and production efficiency. Therefore, if no transfer of exudate was observed on the roller, it was evaluated as a, a case where transfer was observed but the transfer was partial was evaluated as B, and a case where transfer was performed over a wide range was evaluated as C.

A: the surface of the resin sheet was not sticky, nor was there exudate transferred to the roll.

B: the surface of the resin sheet is not sticky, but the exudate is transferred to a partial range of the roller.

C: the resin sheet surface is not tacky, but the exudate is transferred to a large area of the roller.

D: the surface of the resin sheet is sticky.

< flame retardancy >

The flame retardancy of the resin sheets obtained in the examples and comparative examples was evaluated by the following flame retardancy evaluation 1(UL-94VTM test) and flame retardancy evaluation 2 (fire test 45 degree coil method).

< evaluation of flame retardancy 1(UL-94VTM test) >

The flame retardancy of the resin sheets obtained in each example and comparative example was measured according to the UL94 VTM test.

Specifically, the resin sheets obtained in examples and comparative examples were cut into a rectangular shape having a size of 50mm × 200mm ("the japanese text of the rectangular shape" is a "short shape"), to obtain a resin sheet. The resin sheet was allowed to stand at a temperature of 23 ℃ and a relative humidity of 50% for 48 hours or more. The marking was marked at a position 125mm from the lower end of the long side of the resin sheet. Then, an adhesive tape was applied in a range of 125mm to 200mm from the lower end of the long side of the resin sheet, and the short sides were rounded and bonded so as to have a diameter of 13mm, thereby obtaining a cylindrical resin sheet. The obtained cylindrical resin sheet was used as a test piece. The upper end of the test piece was held by a jig and suspended, and 100% cotton of 0.05g or less was placed at a position 300mm below the lower end. In a blue Flame of 105 ml/min and 20mm, a burner having a diameter of 10mm was used, and the Flame (Flame touch) was contacted so that the lower end of the test piece was located at a height of 10mm from the front end of the Flame. After the contact flame was performed for 3 seconds, it was confirmed whether or not the melting of the test piece reached the mark, and at time t1 which was elapsed until the flame on the test piece disappeared, whether or not 100% of the cotton placed below the test piece was burned was confirmed. In the first contact flame, when the melting of the test piece did not reach the mark, the test piece was subjected to the second contact flame in the same manner as in the first contact flame, and the same confirmation as in the first contact flame was performed (the time taken until the fire on the test piece disappeared by the second contact flame was t 2). The series of operations described above starting from cutting the resin sheet into rectangles ("the japanese text of" rectangle "is" short ") was performed for 5 sets in the same resin sheet.

The total time of T1 and T2 was defined as T1, and the total of 5 groups of T1 was defined as T2, and evaluated according to the following criteria. The flame retardancy is preferably D or more, more preferably C or more, further preferably B or more, and particularly preferably a in the following criteria.

A (VTM-0 and T2 for 25 seconds or less): the melting of the test piece did not reach the mark line, T1 and T2 were both 10 seconds or less and T2 was 25 seconds or less, and cotton placed below the test piece did not burn.

B (VTM-0 and T2 is greater than 25 seconds and 50 seconds or less): the melting of the test piece did not reach the marking, T1 and T2 were both 10 seconds or less and T2 was more than 25 seconds and 50 seconds or less, and cotton placed under the test piece did not burn.

C (VTM-1): the melting of the test piece did not reach the mark line, and both T1 and T2 were 30 seconds or less and T2 was 250 seconds or less, and cotton placed below the test piece did not burn.

D (VTM-2): the melting of the test piece did not reach the mark line, and cotton placed below the test piece burned.

E: the melting of the test piece reached the mark (even if the cotton did not burn, the melting reached the mark, belonging to the determination E).

< evaluation of flame retardancy 2 (45 degree coil method in fire test) >

The resin sheets obtained in the examples and comparative examples were subjected to a flame retardancy evaluation test by the "45-degree coil method" specified in rule 4, 3. Specifically, a combustion test was performed by a 45-degree coil method, and the number of contact flames until burnout was measured. Flame retardancy was evaluated according to the following criteria. The flame retardancy is preferably B or more, more preferably a in the following references.

A: more than 4 times

B: 3 times of

C: 2 times or less

< Heat resistance >

The pellets of the resin compositions obtained in the examples and comparative examples were heated in an oven at an atmospheric temperature of 150 ℃ for 7 days, and the color tone and MFR were measured, and the presence or absence of heat resistance of the resin compositions was evaluated based on the amount of change.

(color difference. DELTA.E)

Samples obtained by heating pellets of the resin compositions obtained in examples and comparative examples in an oven set to 150 ℃ in the atmosphere for 7 days and samples stored at normal temperature for the same period of time were prepared. Next, about 5g of each pellet sample was hydraulically press-molded at 230 ℃ using a compression molding machine (manufactured by Toyo Seiki Seisaku-Sho, Ltd., MINI TEST PRESS MP-WC), to obtain a disk-shaped resin sheet for evaluation having a diameter of about 50mm and a thickness of about 2 mm.

Next, the obtained evaluation resin sheet was evaluated by obtaining the brightness L, the color coordinates a, and b before and after heating using a colorimeter (device name: touch panel color computer SM-T, manufactured by Suga tester), calculating the color difference Δ E ab in the system denoted by L a b, and evaluating the color difference Δ E as the color difference Δ E according to the following criteria.

A: a value of [ Delta ] E of 15 or less

B: a value of Delta E of more than 15 and 50 or less

C: delta E values in excess of 50

(MFR ratio)

Pellets obtained by heating pellets of the resin compositions obtained in examples and comparative examples in an oven set to 150 ℃ in the atmosphere for 7 days and pellets stored at normal temperature for the same period of time were prepared. Next, from each pellet, the pellets were subjected to a treatment in accordance with JIS-K7210: 1999 MFR was measured. Next, the ratio of MFR values before and after heating (MFR value after heating/MFR value before heating) was determined, and evaluated according to the following criteria. When the MFR ratio is 1.7 or less, the resin sheet extruded from the T-die does not sag, and moldability is good, which is preferable.

A: MFR ratio of 1.7 or less

B: MFR ratio exceeding 1.7

[ Table 1]

In the column of flash point (. degree.C.), for example, the statement "250 <" means that the flash point is 250 ℃ or higher.

[ Table 2]

[ Table 3]

< conclusion >

From the evaluation results of the resin compositions and resin sheets of examples 1 to 9, it is clear that the resin compositions and resin sheets of the present invention are excellent in flame retardancy and heat resistance, and also excellent in moldability because no stickiness is observed on the surface of the resin sheet. On the other hand, the resin compositions and resin sheets of comparative examples 1 and 2, which did not contain NOR-type HALS compounds, were poor in flame retardancy as a whole. Further, the resin compositions and resin sheets of comparative examples 3 to 9 using a phosphorus-based compound having a flash point lower than a predetermined value were excellent in heat resistance, but poor in flame retardancy or poor in moldability, and the excellent heat resistance and flame retardancy as in examples and the excellent moldability were not compatible with each other, since stickiness was observed on the surface of the resin sheet.

It is found that the resin composition of the present invention can maintain its flame retardancy and heat resistance well even when an inorganic filler is added.

The present application claims priority based on the PCT published on 26.4.2019, i.e., international patent application PCT/JP2019/018032, the entire contents of which are incorporated herein by reference.