JP2023124741A - resin composition - Google Patents

Abstract

To provide a new composition.SOLUTION: A composition is the following (i) or (ii). (i) A composition containing a polycarbonate resin (A) containing a polycarbonate resin (A1) having an alicyclic skeleton, and an acrylic resin (B) having a ring structure, and (ii) a composition containing a polycarbonate resin (A) and an acrylic resin (B) having a ring structure, wherein an absolute value of a difference between a refractive index (wavelength of 589 nm) RA of the polycarbonate resin (A) and a refractive index (wavelength of 589 nm) RB of the acrylic resin (B) is 0.030 or less.SELECTED DRAWING: None

Description

The present invention relates to novel compositions (resin compositions) and the like.

Polycarbonate resin is, for example, a resin that is excellent in high-temperature stability, dimensional stability, impact resistance, rigidity, transparency, and the like.
On the other hand, acrylic resins typified by polymethyl methacrylate (PMMA) are used as optical materials and the like from the viewpoint of high transparency. Among such acrylic resins, acrylic polymers having a ring structure in the main chain are being developed from the viewpoint of heat resistance. For example, Patent Document 1 discloses a copolymer having methyl (meth)acrylate units, methacrylic acid units and glutaric anhydride units.

WO 2017/022393 Pamphlet

An object of the present invention is to provide a novel composition (resin composition) and the like.

As described above, polycarbonate resins and acrylic resins each have excellent physical properties (characteristics), but further novel resins (resin materials) are in demand.

Under such circumstances, the inventors of the present invention have found that a novel resin material (resin composition) can be obtained by combining a specific polycarbonate resin and a specific acrylic resin. For example, we found that it can be used as a resin material (can form a molded product) that has excellent or well-balanced physical properties such as transparency, hardness, heat resistance, and optical properties (low photoelastic coefficient, low retardation expression). We have completed the present invention.

That is, the present invention relates to the following inventions and the like.
[1]
A composition containing a polycarbonate resin (A) containing a polycarbonate resin (A1) having an alicyclic skeleton and an acrylic resin (B) having a ring structure [for example, a polycarbonate containing a polycarbonate resin (A1) having a cyclic skeleton A composition containing a resin (A) and an acrylic resin (B) having a ring structure, wherein the ratio of the acrylic resin (B) is 50% with respect to the total amount of the polycarbonate resin (A) and the acrylic resin (B). % by mass].
[2]
A composition containing a polycarbonate resin (A) and an acrylic resin (B) having a ring structure, wherein the refractive index of the polycarbonate resin (A) (wavelength: 589 nm) _RA and the refractive index of the acrylic resin (B) (wavelength: 589 nm ) in which the absolute value of the difference from R _B is 0.030 or less [for example, a composition containing a polycarbonate resin (A) and an acrylic resin (B) having a ring structure, the acrylic resin (B ) is more than 50% by mass with respect to the total amount of the polycarbonate resin (A) and the acrylic resin (B), and the refractive index (wavelength 589 nm) R _A of the polycarbonate resin (A) and the acrylic resin (B) A composition in which the absolute value of the difference from the refractive index (wavelength 589 nm) _RB is 0.030 or less].
[3]
The composition according to [2], wherein the polycarbonate resin (A) contains a polycarbonate resin (A1) having an alicyclic skeleton.
[4]
The composition according to [1] or [3], wherein the polycarbonate resin (A1) has a structural unit derived from an alicyclic dihydroxy compound.
[5]
The composition according to [1], [3] or [4], wherein the polycarbonate resin (A1) has a structural unit derived from an alicyclic dihydroxy compound represented by the following formula (X).
[6]
The composition according to any one of [1] to [5], wherein the ratio of the polycarbonate resin (A1) having an alicyclic skeleton to the total polycarbonate resin (A) is 30% by mass or more.
[7]
The composition according to any one of [1] to [6], wherein the polycarbonate resin (A) has a refractive index (wavelength of 589 nm) of 1.540 or less.
[8]
The composition according to any one of [1] to [7], wherein the polycarbonate resin (A) has a glass transition temperature of 90 to 140° C., 230° C., and a melt flow rate of 5 to 25 g/10 min under a load of 3.8 kg. .
[9]
The composition according to any one of [1] to [8], wherein the acrylic resin (B) has at least one ring structure selected from a cyclic imide structure, a cyclic amide structure, and a cyclic ester structure.
[10]
The composition according to any one of [1] to [9], wherein the acrylic resin (B) has a cyclic ester structure (lactone ring structure).
[11]
The composition according to any one of [1] to [10], wherein the acrylic resin (B) has a glass transition temperature of 115° C. or higher.
[12]
The acrylic resin (B) according to any one of [1] to [11], wherein the melt flow rate at 230° C. and a load of 3.8 kg is 0.5 to 8 g/10 minutes, and the weight average molecular weight is 50,000 to 200,000. Composition.
[13]
The composition according to any one of [1] to [12], wherein the acrylic resin (B) has a refractive index (wavelength of 589 nm) of 1.492 to 1.510.
[14]
The ratio of the acrylic resin (B) is 55 to 95% by mass with respect to the total amount of the polycarbonate resin (A) and the acrylic resin (B), or the mass of the polycarbonate resin (A) and the acrylic resin (B) The composition according to any one of [1] to [13], wherein the ratio is from 30/70 to 97/3.
[15]
The polycarbonate resin (A) has a refractive index (wavelength of 589 nm) of 1.520 or less and contains a polycarbonate resin (A1) having an alicyclic skeleton at a rate of 30% by mass or more,
The acrylic resin (B) has a refractive index (wavelength of 589 nm) of 1.494 or higher and a glass transition temperature of 120° C. or higher,
The absolute value of the difference between the refractive index (wavelength 589 nm) _RA of the polycarbonate resin (A) and the refractive index (wavelength 589 nm) _RB of the acrylic resin (B) is 0.020 or less,
The ratio of the acrylic resin (B) is 60 to 90% by mass with respect to the total amount of the polycarbonate resin (A) and the acrylic resin (B), or the mass of the polycarbonate resin (A) and the acrylic resin (B) The composition according to any one of [1] to [14], wherein the ratio is from 40/60 to 95/5.
[16]
The composition according to any one of [1] to [15], which is not melt-kneaded (for example, it is a dry blend).
[17]
A molded article comprising the composition according to any one of [1] to [16] {or a molded article formed from the composition [eg, a layered molded article (film, sheet, etc.)]}.
[18]
The molded article according to [17], which is an optical member.
[19]
A decorated molded article [decorative film, for example, a molded article having a multilayer structure (other, for example, a molded article containing at least a base film and a colored layer), wherein at least one layer (especially the base film) has the composition The molded article according to [17] or [18], which is a molded article formed of a material.
[20]
Total light transmittance of 89% or more, haze of 20% or less, pencil hardness of H or more, elongation at break of 40% or more, folding endurance of 80 times or more, trouser tear strength of 50 mN or more, impact strength of 0.22 J or more , a heat shrinkage rate of 0.5% or less, and/or a photoelastic coefficient of 26×10 ⁻¹² /Pa or less, or the composition or molded article according to any one of [1] to [19].
[21]
A method for producing a molded article, comprising the step of molding (for example, melt molding) the composition according to any one of [1] to [16].
[22]
At least the polycarbonate resin (A) and the acrylic resin (B) having a ring structure are mixed (for example, dry blended) without melting to obtain a composition, and this composition (for example, dry blended product) is melt-molded. The method according to [21], which is provided for (used).

According to the present invention, a novel composition (resin composition) can be provided.

Such a composition is a novel composition containing a specific polycarbonate resin and a specific acrylic resin. Although such a composition contains different resins, it is highly dispersible with each other, so not only can the composition (and the molded article) be formed, but also high transparency and low colorability can be achieved.

In particular, in another aspect of the composition of the present invention, while having such high transparency and low colorability (or without impairing it), it is also excellent in various physical properties (for example, high surface hardness, low photoelasticity coefficient, low retardation expression, etc.), and a molded article (molten molded article) can be produced.

Above all, the composition (or the molded article thereof) of such another aspect surprisingly can realize or impart excellent physical properties regardless of the mixing ratio of the specific acrylic resin and the specific polycarbonate. Desired physical properties can be obtained efficiently according to the mixing ratio of each resin.
For example, a composition containing a relatively large amount of a specific acrylic resin [or a molded product thereof (film, sheet, etc.)] has high transparency (and low coloring) and [or high transparency (and low coloring) without compromising], excellent strength can be realized (compatible).
On the other hand, a composition (or a molded product thereof) containing a relatively large amount of a specific polycarbonate resin has high surface hardness (or without impairing high surface hardness) and excellent optical properties (low photoelastic coefficient, low degree of difference expression, etc.) can be realized (compatible).

In another aspect of the present invention, the above molded article (for example, highly transparent molded article) can be provided without subjecting the resin composition to melt-mixing (kneading) in advance. Although the reason for this is not clear, in the present invention, by combining specific resins, it is possible to form a resin composition (and a molded product thereof) even if the resins are not compatible with each other. .
By using such a resin composition, it is possible to reduce the heat history as much as possible, and therefore it is possible to provide a molded article that is advantageous in terms of lower coloring (further transparency) and the like.

The composition (resin composition, further molded article) of the present invention comprises a polycarbonate resin (hereinafter sometimes referred to as polycarbonate resin (A), resin (A), etc.) and an acrylic resin having a ring structure (hereinafter, cyclic acrylic resin (B) having a structure, resin (B), etc.).

[Polycarbonate resin]
Polycarbonate resins (polycarbonate-based resins) include, for example, those having an aliphatic skeleton (alicyclic skeleton, non-alicyclic aliphatic skeleton), those having an aromatic skeleton, those having a combination thereof, and the like. However, it may preferably be a polycarbonate resin having (at least) an aliphatic skeleton.

Polycarbonate resins having such an aliphatic skeleton can easily obtain excellent physical properties such as those described above in addition to high transparency and low colorability when combined with a resin (B) described later.

In addition, by containing an aliphatic skeleton, it is easy to efficiently lower the refractive index of the polycarbonate resin (and further reduce the difference in refractive index with the resin (B) described later), and in addition, the combination with the resin (B) , it is easy to realize the physical properties described above.

In particular, among aliphatic skeletons, alicyclic skeletons are particularly preferable in terms of the balance of physical properties (e.g., heat resistance, strength, etc.). ) (hereinafter sometimes referred to as polycarbonate resin (A1)).

As the polycarbonate resin (A), any resin having a carbonate bond may be used. Generally, a resin containing at least a dihydroxy compound as a polymerization component (having a structural unit derived from a dihydroxy compound) may be used.

Examples of dihydroxy compounds include aliphatic dihydroxy compounds and aromatic dihydroxy compounds.

As the aliphatic dihydroxy compound, an alicyclic dihydroxy compound [for example, an alicyclic dihydroxy compound having a carbon number of 70 or less (eg, 50 or less, 30 or less, about 4 to 20), a 5-membered ring or a 6-membered ring structure at least alicyclic dihydroxy compound having 70 or less carbon atoms (e.g., 50 or less, 30 or less, about 4 to 20) and having at least a 5- or 6-membered ring structure], non-alicyclic Formula (aliphatic) dihydroxy compounds and the like are included.

Alicyclic dihydroxy compounds include, for example, cycloalkanediols {or dihydroxycycloalkanes, such as mono (monocyclic) cycloalkanediols [eg, cyclohexanediols (eg, 1,2-cyclohexanediol, 1 C _4-10 (mono)cycloalkanediols such as ,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol)], poly(polycyclic)cycloalkanediols or bridged cyclic cycloalkanediols [e.g., tricyclodecanediol, pentacyclopentadecanediol, decalindiol (or tricyclotetradecanediol, such as 2,6-decanediol, 1,5-decanediol, 2,3 -decalindiol), norbornanediol (e.g., 2,3-norbornanediol, 2,5-norbornanediol), adamantanediol (e.g., 1,3-adamantanediol), etc.}, di(hydroxyalkyl)cycloalkanes {or cycloalkanedialkanols, such as mono(monocyclic) cycloalkanedialkanols [e.g., cyclohexanedimethanols (e.g., 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 C _4-10 (mono)cycloalkane di-C _1-4 alkanols such as -cyclohexanedimethanol)], poly(polycyclic) cycloalkane dialkanols or bridged cyclic cycloalkane dialkanols [for example, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol (or tricyclotetradecanedimethanol, such as 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol), norbornanedimethanol (e.g., 2,3-norbornanedimethanol, 2,5-norbornanedimethanol), adamantanedimethanol (e.g., 1,3-adamantanedimethanol), etc.}, heterocyclic aliphatic dihydroxy compounds { For example, heteromonocyclic aliphatic didroxy compounds (e.g., tetrahydrofuran-2,2-dimethanol, etc.), heteropolycyclic aliphatic dihydroxy compounds [e.g., compounds represented by the following formula (X), oxacyclospiroalkane Compounds having a skeleton (e.g., 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1 -dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetra oxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane), etc.} etc.

Examples of the compound represented by the above formula (X) (compound (X)) include isosorbide, isomannide, and isoidet. Compound (X) may be a mixture (isomer mixture). Compound (X) may contain at least isosorbide.

Non-alicyclic dihydroxy compounds include, for example, alkanediols (e.g., ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1, _C2-20 alkanediols such as 2-butanediol, 1,5-heptanediol, 1,6-hexanediol), polyalkanediols (e.g. polyC2 such as diethylene glycol, triethylene glycol, tetraethylene glycol, etc. _{) -6} alkanediols) and the like.

You may use an aliphatic dihydroxy compound individually or in combination of 2 or more types.

Examples of aromatic dihydroxy compounds include biphenols (eg, 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl), bisphenols {eg, bis (Hydroxyphenyl)alkanes [for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromo phenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4′-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1, bis(hydroxyphenyl)C _1-10 alkanes such as 1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane], bis(hydroxyphenyl)cycloalkanes [for example, 1 bis(hydroxyphenyl)C _4-20 cycloalkanes such as ,1-bis(4-hydroxyphenyl)cyclohexane], bis(hydroxyphenyl)sulfones [e.g. bis(4-hydroxyphenyl)sulfone, 2,4′ -dihydroxydiphenyl sulfone], bis(hydroxyphenyl) ethers [e.g. 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 4,4′-dihydroxy-2,5- diethoxydiphenyl ether], bis (hydroxyphenyl) sulfides [e.g., bis (4-hydroxyphenyl) sulfide, etc.], bis (hydroxyphenyl) ketones [e.g., bis (4-hydroxyphenyl) ketone, etc.], fluorene skeleton dihydroxy compounds {for example, bis(hydroxyphenyl)fluorenes [for example, 9,9-bis(4-hydroxyphenyl)fluorene], bis(hydroxyalkoxy)fluorenes [for example, 9,9-bis(4-(2 9,9-bis[(hydroxy-C _2-4 alkoxy)phenyl]fluorenes] such as -hydroxyethoxy)phenyl)fluorene and 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene } etc. are mentioned.

You may use an aromatic dihydroxy compound individually or in combination of 2 or more types.

You may use a dihydroxy compound individually or in combination of 2 or more types.

As described above, the polycarbonate resin preferably has at least an aliphatic skeleton (especially an alicyclic skeleton), so the dihydroxy compound also contains at least an aliphatic dihydroxy compound (especially an alicyclic dihydroxy compound). is preferred.

Among the alicyclic dihydroxy compounds (derived structural units), the compound represented by the formula (X) (e.g., isosorbide) (derived structural units) has transparency and other physical properties, as well as the acrylic resin (B). (for example, it is easy to reduce the difference from the glass transition temperature of the acrylic resin (B)). Therefore, the polycarbonate resin may have at least structural units derived from the compound represented by the formula (X).

In the dihydroxy compound containing an aliphatic dihydroxy compound, the ratio of the aliphatic dihydroxy compound to the total dihydroxy compound can be selected according to the type and desired physical properties (further refractive index), etc., but for example, 1 mol% or more ( For example, 5 mol% or more), preferably 10 mol% or more (e.g., 20 mol% or more), more preferably 30 mol% or more (e.g., 40 mol% or more), or 50 mol% or more (e.g., , 60 mol % or more, 70 mol % or more, 80 mol % or more, 90 mol % or more, 95 mol % or more, (substantially) 100 mol %).

When the aliphatic dihydroxy compound contains an alicyclic dihydroxy compound, the ratio of the alicyclic dihydroxy compound to the total aliphatic dihydroxy compound can be selected depending on the type and desired physical properties (further refractive index). , For example, 10 mol% or more (e.g., 30 mol% or more), preferably 50 mol% or more (e.g., 60 mol% or more), more preferably 70 mol% or more (e.g., 80 mol% or more) It may be 85 mol % or more (eg, 90 mol % or more, 93 mol % or more, 95 mol % or more, 98 mol % or more, (substantially) 100 mol %).

When the alicyclic dihydroxy compound contains the compound represented by the formula (X) (compound (X)), the ratio of the compound (X) to the entire alicyclic dihydroxy compound can be adjusted to achieve desired physical properties (further refraction For example, 1 mol% or more (e.g., 2 mol% or more), preferably 3 mol% or more (e.g., 5 mol% or more), more preferably 7 mol% or more (e.g., 10 mol% or more), 100 mol% or less (e.g., (substantially) 100 mol%, 99 mol% or less, 98 mol% or less, 97 mol% or less, 96 mol% or less, 95 mol% 94 mol % or less, 93 mol % or less, 90 mol % or less).

As described above, the polycarbonate-based resin usually contains at least a dihydroxy compound as a polymerized component, but such a polymerized component may optionally contain other polymerized components in addition to the dihydroxy compound. good.

Such other polymerization components include, for example, compounds having 3 or more hydroxy groups {e.g., aromatic polyhydroxy compounds [e.g., phloroglucin, 4,6-dimethyl-2,4,6-tris(4-hydroxy phenyl)heptene-2, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-3, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyaryl)oxindole, 5-chlorisatin, 5, 7-dichlorisatin, 5-bromyisatin], etc.} and the like.

You may use another polymerization component individually or in combination of 2 or more types.

When the polycarbonate resin has structural units derived from other polymerized components (compounds having 3 or more hydroxy groups), the entire dihydroxy compound and other polymerized components (compounds having 3 or more hydroxy groups) (derived structural units) The ratio of other polymerization components (compounds having 3 or more hydroxy groups) (derived structural units) is, for example, 10 mol% or less (e.g., 5 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less), or 0.001 mol% or more (e.g., 0.005 mol% or more, 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, etc.) may be

Incidentally, the polycarbonate resin is usually thermoplastic (resin).

You may use polycarbonate-type resin individually or in combination of 2 or more types.

Among them, the polycarbonate-based resin (A) preferably contains at least a polycarbonate resin having an aliphatic skeleton (in particular, a polycarbonate resin (A1) having an alicyclic skeleton), as described above.

In such a polycarbonate resin (A), the ratio of the polycarbonate resin having an aliphatic skeleton to the total polycarbonate resin (A) is, for example, 1% by mass or more (e.g., 5% by mass or more), preferably 10% by mass or more. (e.g., 20% by mass or more), more preferably 30% by mass or more (e.g., 40% by mass or more), and 50% by mass or more (e.g., 60% by mass or more, 70% by mass or more, 80% by mass) 90% by mass or more, 95% by mass or more, or (substantially) 100% by mass).

In particular, when the polycarbonate resin (A) contains the polycarbonate resin (A1) having an alicyclic skeleton, the ratio of the polycarbonate resin (A1) having an alicyclic skeleton to the total polycarbonate resin (A) is, for example, 10. % by mass or more (e.g., 20% by mass or more), preferably 30% by mass or more (e.g., 40% by mass or more), more preferably 50% by mass or more (e.g., 60% by mass or more), or 70% by mass % or more (for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, (substantially) 100% by mass).

When the polycarbonate resin having an aliphatic skeleton contains the polycarbonate resin (A1) having an alicyclic skeleton, the ratio of the polycarbonate resin (A1) having an alicyclic skeleton to the total polycarbonate resin having an aliphatic skeleton is It can be selected according to the type and desired physical properties (further refractive index) etc. Preferably, it may be 70% by mass or more (e.g., 80% by mass or more), 85% by mass or more (e.g., 90% by mass or more, 93% by mass or more, 95% by mass or more, 98% by mass or more, (substantially 2) 100% by mass).

When the polycarbonate resin (A1) having an alicyclic skeleton contains a polycarbonate resin having a structural unit derived from the compound (X), the total polycarbonate resin (A1) having an alicyclic skeleton is The ratio of the polycarbonate resin having a structural unit can be selected depending on the desired physical properties (further refractive index) and the like. , 5% by mass or more), more preferably 7% by mass or more (e.g., 10% by mass or more), and 100% by mass or less (e.g., (substantially) 100% by mass, 99% by mass or less, 98% by mass or less). % by mass, 97% by mass or less, 96% by mass or less, 95% by mass or less, 94% by mass or less, 93% by mass or less, 90% by mass or less).

The melt flow rate (sometimes referred to as M _A ) of the polycarbonate resin (A) depends on its type and composition, but at a temperature of 230° C. and a load of 3.8 kg, for example, 0.1 to 50 g/10 minutes (for example, 0.5 to 45 g/10 min), preferably 1 to 40 g/10 min (eg, 2 to 35 g/10 min), more preferably 3 to 30 g/10 min (eg, 5 to 25 g/10 min). There may be.

The melt flow rate of polycarbonate resin may be measured according to JIS K 7210.

The shear viscosity (sometimes referred to as _VA ) of the polycarbonate resin (A) depends on its type and composition, but at a temperature of 240° C. and a shear rate of 1000/s, it is, for example, 100 to 500 Pa s, preferably 120 to 480 Pa. ·s (for example, 130 to 450 Pa·s), more preferably about 150 to 400 Pa·s.

Specifically, the shear viscosity of the polycarbonate resin may be measured by the method described below.

The glass transition temperature (Tg) (sometimes referred to as Tg _A ) of the polycarbonate resin (A) depends on its type and composition, but is, for example, 70 to 200°C, preferably 80 to 160°C, more preferably 90 to 140. °C (eg, 95 to 130°C).

In addition, Tg may be measured, for example, by the method described later.

The refractive index (wavelength 589 nm) (sometimes referred to as _RA ) of the polycarbonate resin (A) depends on its type and composition, but is, for example, 1.650 or less (eg, 1.600 or less), preferably 1.580. or less (eg, 1.560 or less), more preferably 1.550 or less (eg, 1.540 or less), or 1.530 or less (eg, 1.520 or less, 1.515 or less, 1.540 or less). 510 or less, 1.505 or less, 1.502 or less, 1.500 or less).

The refractive index may be a value at 23° C., and may be measured, for example, by the method described later.

As the polycarbonate resin (A), a commercially available product may be used, or one produced by a conventional method may be used.

For example, the polycarbonate resin may be produced by any of a phosgene method (e.g., a solution polymerization method using phosgene), a method using a carbonic acid diester (e.g., a melt polymerization method in which the reaction is performed with a carbonic acid diester), and the like. may be produced by a method using a carbonic acid diester.

In the method using such a diester carbonate, for example, a dihydroxy compound [and optionally other polymerization components ( compounds having 3 or more hydroxy groups)], carbonic acid diesters [e.g., diaryl carbonates (e.g., diphenyl carbonate, ditolyl carbonate, etc.), dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate)] etc.] and react [polymerization (solution polymerization)].

[acrylic resin]
Acrylic resin (acrylic polymer) has a ring structure. Such acrylic resins are usually thermoplastic (resins, polymers). The method for producing such an acrylic resin is not particularly limited, but the acrylic resin may be produced by the method described below.

Acrylic resins (sometimes referred to as acrylic resin (B), resin (B), etc.) usually have (meth)acrylic acid ester units [(meth)acrylic acid ester-derived units (structural units)]. good too.

The (meth)acrylic acid ester constituting the (meth)acrylic acid ester unit is not particularly limited, but examples thereof include aliphatic (meth)acrylates [e.g. C _1-18 alkyl (meth)acrylates such as methyl, ethyl (meth)acrylate, and butyl (meth)acrylate], alicyclic (meth)acrylates [for example, cycloalkyl (meth)acrylates ( For example, cyclopropyl (meth)acrylate, _C3-20 cycloalkyl (meth)acrylate such as cyclobutyl (meth)acrylate), bridged cyclic (meth)acrylate (e.g., isobornyl (meth)acrylate), etc.] , aromatic (meth)acrylates [e.g., aryl (meth)acrylates (e.g., C _6-20 aryl (meth)acrylates such as phenyl (meth)acrylate and o-tolyl (meth)acrylate), ( meth)acrylic acid aralkyl ester (e.g. C _6-10 aryl C _1-4 alkyl (meth)acrylate such as benzyl (meth)acrylate), phenoxyalkyl (meth)acrylate (e.g. phenoxy (meth)acrylate (phenoxy C _1-4 alkyl (meth)acrylate such as ethyl), etc.] and the like.

(Meth)acrylic acid esters also include (meth)acrylic acid esters having a substituent (eg, a hydroxy group, an alkoxy group, a glycidyl group, etc.). Examples of such (meth)acrylic acid esters include methacrylic acid esters having a hydroxy group [e.g., (meth)acrylic acid hydroxyalkyl esters (e.g., (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate)]. acid hydroxy C _1-12 alkyl), etc.], (meth)acrylic acid esters having an alkoxy group [e.g., (meth)acrylic acid alkoxyalkyl esters (e.g., methacrylic acid C ₁ such as 2-methoxyethyl (meth)acrylate, etc.) _-12 alkoxy C _1-12 alkyl, etc.)], (meth)acrylic acid esters having a glycidyl group (eg, glycidyl (meth)acrylate, etc.), and the like.

The (meth)acrylic acid ester may constitute a (meth)acrylic acid ester unit either singly or in combination of two or more.

The (meth)acrylic acid ester unit preferably contains at least a methacrylic acid ester unit, depending on the desired physical properties.

Examples of methacrylic acid esters constituting (meth)acrylic acid ester units include aliphatic methacrylates [e.g., methacrylic acid alkyl esters (e.g., methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methacrylic n-butyl acid, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, C _1-18 alkyl methacrylates such as octyl methacrylate, decyl methacrylate, dodecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate and octadecyl methacrylate, preferably C _1-12 alkyl methacrylate), etc.], Alicyclic methacrylates [e.g., cycloalkyl methacrylates (e.g., C _3-20 cycloalkyl methacrylates such as cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, preferably C _3-12 methacrylate, cycloalkyl), bridged cyclic methacrylates (e.g., isobornyl methacrylate, etc.), etc.], aromatic methacrylates [e.g., aryl methacrylates (e.g., phenyl methacrylate, o-tolyl methacrylate, m-tolyl methacrylate, methacrylic acid p-Tolyl, 2,3-xylyl methacrylate, 2,4-xylyl methacrylate, 2,5-xylyl methacrylate, 2,6-xylyl methacrylate, 3,4-xylyl methacrylate, 3,5-methacrylate C _6-20 aryl methacrylates such as xylyl, 1-naphthyl methacrylate, 2-naphthyl methacrylate, binaphthyl methacrylate and anthryl methacrylate, preferably C _6-10 aryl methacrylates), aralkyl methacrylates (for example, methacrylic acid C _6-10 aryl C _1-4 alkyl methacrylate such as benzyl acid), phenoxyalkyl methacrylate (eg, phenoxy C _1-4 alkyl methacrylate such as phenoxyethyl methacrylate), etc.].

Among methacrylic acid ester units, the (meth)acrylic acid ester unit preferably contains at least a methacrylic acid alkyl ester unit (for example, a methacrylic acid C _1-18 alkyl unit) from the viewpoint of improving transparency. In particular, it is more preferable to contain at least a methyl methacrylate unit.

The acrylic resin may optionally contain units derived from other polymerizable monomers (monomers) other than the (meth)acrylic acid ester units. Such other monomers include, for example, acid group-containing monomers (methacrylic acid, acrylic acid, etc.), styrenic monomers [e.g., styrene, vinyltoluene, substituents (e.g., halogen groups, alkoxy groups, alkyl groups, hydroxy groups, etc.) (e.g., α-methylstyrene, chlorostyrene, etc.), styrenesulfonic acid or salts thereof], vinyl esters (e.g., vinyl acetate, etc.), unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.) ), olefinic monomers (e.g., C _2-10 alkenes such as ethylene, propylene, 1-butene, isobutylene, 1-octene), amide group-containing vinylic monomers [e.g., (meth)acrylamide, N-substituted ( meth)acrylamide (e.g., N-alkyl (meth)acrylamide such as N-methyl (meth)acrylamide; N-cycloalkyl (meth)acrylamide such as N-cyclohexyl (meth)acrylamide; N-phenyl (meth)acrylamide and the like N-aryl(meth)acrylamide; N-aralkyl(meth)acrylamide such as N-benzyl(meth)acrylamide, etc.], 2-(hydroxymethyl)acrylate (e.g., ethyl 2-(hydroxymethyl)acrylate alkyl esters such as ) and the like.

Other monomers may be used singly or in combination to form units derived from other monomers.

The content of the (meth)acrylate unit in the acrylic resin (or the structural unit of the acrylic resin) can be selected, for example, from a range of 10% by mass or more (e.g., 20% by mass or more), preferably 30% by mass or more. (e.g., 35% by mass or more), more preferably 40% by mass or more (e.g., 45% by mass or more), 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, etc. may be

When the acrylic resin contains a methacrylic acid ester unit, the content of the methacrylic acid ester unit in the acrylic resin (or the structural unit of the acrylic resin) can be selected, for example, from a range of 10% by mass or more, preferably 20% by mass or more. is 30% by mass or more (e.g., 35% by mass or more), more preferably 40% by mass or more (e.g., 45% by mass or more), 50% by mass or more, 55% by mass or more, 60% by mass or more, It may be 65% by mass or more.

When the acrylic resin contains a methacrylate ester unit, the content of the methacrylate unit in the (meth)acrylate unit is, for example, 10% by mass or more (e.g., 20% by mass or more), preferably 30% by mass or more. (e.g., 40% by mass or more), more preferably 50% by mass or more (e.g., 60% by mass or more), or 70% by mass or more, 80% by mass or more, 90% by mass or more, etc. .

When the acrylic resin contains a methacrylic acid alkyl ester unit, the content of the methacrylic acid alkyl ester unit in the (meth)acrylic acid ester unit is, for example, 10% by mass or more (e.g., 20% by mass or more), preferably 30% by mass. % or more (e.g., 40% by mass or more), more preferably 50% by mass or more (e.g., 60% by mass or more), and 70% by mass or more, 80% by mass or more, 90% by mass or more, etc. good too.

When the acrylic resin contains a methyl methacrylate unit, the content of the methyl methacrylate unit in the (meth)acrylate unit is, for example, 10% by mass or more (e.g., 20% by mass or more), preferably 30% by mass. % or more (e.g., 40% by mass or more), more preferably 50% by mass or more (e.g., 60% by mass or more), and 70% by mass or more, 80% by mass or more, 90% by mass or more, etc. good too.

When the acrylic resin contains an acrylate unit, the content of the acrylate unit in the acrylic resin may be relatively small from the viewpoint of heat resistance and refractive index, for example, less than 10% by mass (e.g., 8% by mass % or less), preferably 5% by mass or less (eg, 4% by mass or less), more preferably 3% by mass or less (eg, 2% by mass or less).

When the acrylic resin contains units derived from other polymerizable monomers (monomers), the content ratio of the units in the acrylic resin is not particularly limited and can be appropriately selected. In particular, when an acid group-containing monomer is included as another polymerizable monomer, the content of the acid group-containing monomer unit may be relatively small from the viewpoint of transparency, coloration, etc., for example, 10% by mass or less. (eg, 5% by mass or less), preferably 2% by mass or less (eg, 1% by mass or less), more preferably 0.5% by mass or less.

Acrylic resin (B) has a ring structure. This ring structure is usually present in the main chain of an acrylic resin (polymer chain, acrylic polymer).

In addition, due to the acrylic resin having a ring structure, various physical properties [for example, heat resistance, moist heat resistance, yellowing resistance, hardness (strength), solvent resistance, surface hardness, oxygen and water vapor barrier properties, optical properties, dimensional stability, shape stability, etc.] can be imparted, improved or enhanced.
In addition, since the acrylic resin has a ring structure, it becomes possible to efficiently produce molded articles (for example, films, sheets, lenses) having a thinner film thickness than polymethyl methacrylate or the like.

Specific ring structures include, for example, cyclic imide structures (e.g., structures derived from N-substituted maleimide monomers, glutarimide structures, etc.), cyclic amide structures (e.g., lactam structures, etc.), cyclic ester structures (e.g., lactone ring structure, etc.), an acid anhydride structure (for example, a structure derived from a maleic anhydride monomer, a glutaric anhydride structure), and the like.

The ring structure is particularly a non-acid anhydride structure [e.g., a structure derived from a maleic anhydride monomer, a ring structure other than a glutaric anhydride structure (e.g., a cyclic imide structure, a cyclic amide structure, a cyclic ester structure, etc.)]. may

The acrylic resin may have one or more ring structures. In the case of having two or more ring structures, the two or more ring structures may be ring structures of the same system (e.g., cyclic imide structures of two or more types), or ring structures of different systems (e.g., , a combination of a cyclic imide structure and a lactone structure, etc.).

Examples of the glutarimide structure and the glutaric anhydride structure include structures represented by the following formula (1).

(wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group, R ³ is a hydrogen atom or a substituent, X ¹ is an oxygen atom or a nitrogen atom, ^{X 1} is an oxygen n=0 when it is an atom, and n=1 when ^X1 is a nitrogen atom.)

Examples of alkyl groups for R ¹ and R ² in formula (1) include C _1-8 alkyl groups (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, 2-ethylhexyl group, etc.).

R ¹ and R ² are particularly preferably hydrogen atoms or C _1-4 alkyl groups.

Examples of substituents for R ³ in formula (1) include hydrocarbon groups.
Examples of hydrocarbon groups include aliphatic groups, alicyclic groups, and aromatic groups. The hydrocarbon group may further have a substituent such as halogen.

In R ³ of formula (1), the aliphatic group includes, for example, a C _1-10 alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, 2-ethylhexyl group, etc.). Among these alkyl groups, C _1-4 alkyl groups, particularly methyl groups, are preferred.

In R ³ of formula (1), the alicyclic group includes, for example, a C _3-12 cycloalkyl group (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.). Among these cycloalkyl groups, a C _3-7 cycloalkyl group, particularly a cyclohexyl group, is preferred.

In R ³ of formula (1), the aromatic group includes, for example, a C _6-20 aromatic group [e.g., a C _6-20 aryl group (e.g., phenyl group, o-tolyl group, m-tolyl group, p -tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group , 2-naphthyl group, binaphthyl group, anthryl group, etc.), C _7-20 aralkyl group (eg, benzyl group, etc.), etc.]. Among these aromatic groups, a phenyl group and a tolyl group are preferred.

Typically, in formula (1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a C _1-10 alkyl group, a C _3-12 cycloalkyl group or a C _6-20 It may be an aromatic group, preferably R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a C _1-4 alkyl group, a C _3-7 cycloalkyl group, a C _{6- 20} aryl group or C _7-20 aralkyl group, more preferably R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ is a methyl group, a cyclohexyl group, a phenyl group or a tolyl group and most preferably, R ¹ and R ² may each independently be a hydrogen atom or a methyl group, and R ³ may be a cyclohexyl group or a phenyl group. From the viewpoint of suppressing coloring of the acrylic polymer, ^R3 may be a hydrogen atom, a methyl group, or a cyclohexyl group, and from the viewpoint of improving the strength of the molded article, ^R3 may be a hydrogen atom or a methyl group.

The ring structure may have one or more of the structures represented by formula (1).

In particular, when the ring structure has a structure represented by formula (1), it has a glutarimide structure that is a cyclic non-anhydride structure (i.e., a structure in which X ¹ is a nitrogen atom in formula (1)). is preferred.

In addition, the glutaric anhydride structure (that is, the structure in which X ¹ is an oxygen atom in formula (1)) is hydrolyzed, the acid value increases, the water resistance and hot water resistance decrease, and the optical properties change. There is a risk of Therefore, it may be preferred that the ring structure has substantially no glutaric anhydride structure, or contains only a small amount of glutaric anhydride structure.

Examples of structures derived from maleimide monomers (especially N-substituted maleimide monomers) and maleic anhydride monomers include structures represented by the following formula (2).

(wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group, R ⁶ is a hydrogen atom or a substituent, X ² is an oxygen atom or a nitrogen atom, ^{X 2} is an oxygen atom n=0 when X2 is a nitrogen atom, and n=1 when ^X2 is a nitrogen atom.)

Examples of substituents for R ⁶ in formula (2) include hydrocarbon groups.
Examples of the hydrocarbon group include aliphatic groups {e.g., alkyl groups [e.g., C _1-6 linear alkyl groups (e.g., methyl group, ethyl group, etc.), C _1-6 branched alkyl groups (e.g., isopropyl C _1-6 alkyl groups such as groups), etc.], alicyclic groups (e.g., C _3-20 cycloalkyl groups such as cyclopentyl group, cyclohexyl group, etc.), aromatic groups {e.g., C _6-20 aromatic groups [eg, C _7-20 aralkyl group (eg, benzyl group, etc.), C _6-20 aryl group (eg, phenyl group, etc.)]} and the like. The hydrocarbon group may further have a substituent such as halogen.

When ^X2 is an oxygen atom, the ring structure represented by formula (2) is a structure derived from a maleic anhydride monomer.

On the other hand, when ^X2 is a nitrogen atom, the ring structure represented by formula (2) is a structure derived from an N-substituted maleimide monomer.

In formula (2), when X ² is a nitrogen atom, preferably R ⁴ and R ⁵ are each independently a hydrogen atom, and R ⁶ is a C _3-20 cycloalkyl group or a C _6-20 aromatic group. more preferably, R ⁴ and R ⁵ may each independently be a hydrogen atom, and R ⁶ may be a cyclohexyl group, a benzyl group or a phenyl group. From the viewpoint of suppressing coloring of the acrylic polymer, ^R6 may be a hydrogen atom, a methyl group, or a cyclohexyl group, and from the viewpoint of improving the strength of the molded article, ^R6 may be a hydrogen atom or a methyl group.

The ring structure may have one or more structures represented by formula (2).

In particular, when the ring structure has a structure represented by formula (2), a structure derived from a maleimide monomer that is a cyclic non-acid anhydride structure (i.e., a structure in which ^X2 is a nitrogen atom in formula (2) ).

In addition, in the above formula (2), when ^X2 is an oxygen atom (and n=0), the above formula (2) becomes a structure derived from a maleic anhydride monomer. Such a structure derived from a maleic anhydride monomer may be hydrolyzed, or may have an increased acid value, degrading water resistance and hot water resistance, or altering optical properties. Therefore, it may be preferred that the ring structure has substantially no structure derived from the maleic anhydride monomer or contains only a small amount of structure derived from the maleic anhydride monomer.

The lactone ring structure is not particularly limited, and may be, for example, a 4- to 8-membered ring. is more preferable.

The lactone ring structure may be, for example, a structure disclosed in JP-A-2004-168882, and examples thereof include structures represented by the following formula (3).

(Wherein R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a substituent.)

In formula (3), examples of substituents include organic residues such as hydrocarbon groups.
Examples of the hydrocarbon group include aliphatic groups (e.g., C _1-20 alkyl groups such as methyl group, ethyl group and propyl group; C _2-20 unsaturated aliphatic hydrocarbon groups such as ethenyl group and propenyl group; etc.), aromatic groups (eg, C _6-20 aromatic hydrocarbon groups such as phenyl group, naphthyl group, etc.), and the like.

The hydrocarbon group may contain an oxygen atom, and one or more hydrogen atoms may be substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group and an ester group.

In formula (3), preferably R ⁹ is a hydrogen atom or a methyl group, R ⁷ and R ⁸ may each independently be a hydrogen atom or a C _1-20 alkyl group, more preferably R ⁹ is A hydrogen atom or a methyl group, R ⁷ and R ⁸ may each independently be a hydrogen atom or a methyl group.

The ring structure may contain one or more structures represented by formula (3).

The lactam ring structure is not particularly limited and includes, for example, a pyrrolidinone ring structure represented by the following formula (4).

The pyrrolidinone ring structure has a five-membered amide ring structure (cyclic amide structure) as a basic skeleton. This cyclic amide structure is also a five-membered ring lactam structure (γ-lactam structure). Having a pyrrolidinone ring structure in the main chain means that at least one of the five atoms constituting the basic skeleton of the five-membered pyrrolidinone ring structure, typically an amide bond (-N (R) CO-) is located in the main chain of the polymer and constitutes the main chain.

(In the formula, R ¹⁰ to R ¹² are each independently a hydrogen atom or a substituent.)

Examples of substituents for R ¹⁰ in formula (4) include a hydrocarbon group and a —NHCOR ¹³ group (R ¹³ is a hydrogen atom or a hydrocarbon group).

The hydrocarbon group for R ¹⁰ or R ¹³ includes, for example, an aliphatic group, an alicyclic group, an aromatic group and the like.
Aliphatic groups include, for example, C _1-18 alkyl groups (e.g., C _1-18 linear or branched groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups). alkyl group, etc.).
The alicyclic group includes, for example, a C _3-18 cycloalkyl group (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.) and the like.
The aromatic group includes, for example, a C _6-20 aromatic group [e.g., a C _6-20 aryl group (e.g., phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, etc.), C _7-20 aralkyl group, (e.g., benzyl group, etc.), etc.].

R ¹⁰ is particularly preferably a hydrogen atom, a C _1-18 straight chain alkyl group (eg, methyl group, etc.), or the like.
Further, as R ¹³ , in particular, a hydrogen atom, a C _1-18 linear alkyl group (preferably a C _1-12 linear alkyl group, more preferably a C _1-4 linear alkyl group, etc.), C _{6 -20} aryl group (eg, phenyl group etc.), C _3-18 cycloalkyl group (preferably C _3-12 cycloalkyl group, more preferably C _3-6 cycloalkyl group etc.) and the like are preferred.

Examples of substituents for R ¹¹ in formula (4) include —COOR ¹⁴ group (R ¹⁴ is a hydrogen atom or a hydrocarbon group).

Examples of the hydrocarbon group for R ¹⁴ include the hydrocarbon groups exemplified for R ¹⁰ and R ¹³ .
Moreover, the particularly preferred embodiment of R ¹⁴ is also the same as the particularly preferred embodiment of R ¹³ .

Examples of substituents for R ¹² in formula (4) include —COR ¹⁵ groups (R ¹⁵ is a hydrogen atom or a hydrocarbon group).

Examples of the hydrocarbon group for R ¹⁵ include the hydrocarbon groups exemplified for R ¹⁰ and R ¹³ .
Moreover, the particularly preferred embodiment of R ¹⁵ is also the same as the particularly preferred embodiment of R ¹³ .

The ring structure of the acrylic resin has the desired physical properties (for example, heat resistance, hardness (strength), solvent resistance, surface hardness, oxygen and water vapor barrier properties, optical properties, dimensional stability, shape stability, etc.). It may be selected as appropriate. For example, from the viewpoint of heat resistance, the ring structure may preferably contain a lactone ring structure, a cyclic imide structure (eg, a structure derived from an N-substituted maleimide monomer, a glutarimide structure, etc.).

In addition, from the viewpoint of water resistance and hot water resistance, the ring structure should be a cyclic non-anhydride structure [eg, a lactone ring structure, a cyclic imide structure (especially a glutarimide structure, a structure derived from an N-substituted maleimide monomer)]. may be suitably included.

Furthermore, from the viewpoint of surface hardness, solvent resistance, barrier properties, optical properties, etc., the ring structure may preferably contain a lactone ring structure, a glutarimide structure, and the like.

In particular, the ring structure may contain at least one ring structure selected from cyclic imide structures (especially glutarimide structures, structures derived from N-substituted maleimide monomers) and lactone ring structures, particularly It may contain at least a lactone ring structure. With such a ring structure, it is easy to adjust the balance of various physical properties (for example, heat resistance and refractive index) in combination with the polycarbonate resin (A).

The content ratio of the ring structure can be selected depending on the application, desired physical properties, etc., and is not particularly limited. 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, or 10% by mass or more, 15% by mass or more, 20% by mass or more, and the like.

The content of the ring structure (or its upper limit) is not particularly limited, and is, for example, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less in the acrylic resin. % by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or the like.

A higher content of the ring structure is preferable in terms of heat resistance, hardness (strength), solvent resistance, surface hardness, dimensional stability, and the like.

An appropriate range (for example, 1 to 70% by mass, 3 to 60% by mass, 5 to 60% by mass, 5 to 50% by mass, etc.) may be set by appropriately combining these upper and lower limits. Good (and so on).

In particular, when the acrylic resin has a glutarimide structure, the content of the glutarimide structure is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. % by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

When the acrylic resin has a structure derived from the N-substituted maleimide monomer, the content of the structure derived from the N-substituted maleimide monomer is, for example, 5 to 90% by mass, preferably 5 to 60% by mass, more preferably. may be 10 to 50% by mass, more preferably 10 to 30% by mass.

When the acrylic resin has a lactone ring structure, the content of the lactone ring structure is, for example, 1 to 80% by mass, preferably 3 to 70% by mass, more preferably 5 to 60% by mass (for example, 10 to 50% by mass %), 15% by mass or more (eg, 18 to 55% by mass), 20% by mass or more (eg, 23 to 50% by mass), 25% by mass or more (eg, 26 to 45% by mass, 28 ~40% by mass, etc.).

When the acrylic resin has a lactam ring structure, the content of the lactam ring structure may be, for example, about 1 to 80% by mass, preferably 5 to 70% by mass, more preferably about 10 to 50% by mass.

In addition, the content of the ring structure may be, for example, 1 to 80% by mass, preferably 3 to 70% by mass, more preferably 5 to 60% by mass (eg, 10 to 50% by mass). High percentage, for example, 10% by mass or more [for example, 13 to 60% by mass, 15% by mass or more (eg, 18 to 55% by mass), 20% by mass or more (eg, 23 to 50% by mass), 25% by mass or more (eg, 26 to 45% by mass, 28 to 40% by mass, etc.)].

By making the content of the ring structure introduced into the acrylic resin relatively high, it is easy to efficiently obtain a resin composition having extremely excellent heat resistance (for example, a high glass transition temperature) and resistance to moist heat.

The composition of the present invention can efficiently suppress coloring (yellowing) even when the acrylic resin contains a high proportion of a ring structure (for example, a ring structure containing at least a lactone ring structure).

The ratio of the ring structure in the acrylic resin can be determined by a conventional method depending on the type of the ring structure. For example, the ratio of the cyclic ester structure (lactone ring structure) can be determined based on the dealcoholization reaction rate Alternatively, the ratio of non-cyclic ester structures (eg, cyclic imide structures, cyclic amide structures, acid anhydride structures, etc.) may be determined based on NMR (eg, ¹ H-NMR, ¹³ C-NMR, etc.) analysis. . In NMR analysis ( _{NMR measurement} ), analysis (measurement) conditions can be selected as appropriate. may be analyzed (measured) with

As an example, a method based on the dealcoholization reaction rate will be described.

First, based on the amount of weight loss that occurs when all the hydroxyl groups are dealcoholized as methanol from the polymer composition obtained by polymerization, from 150 ° C. before the start of weight loss in dynamic TG measurement to before the decomposition of the polymer starts. The dealcoholization reaction rate was obtained from the weight reduction due to the dealcoholization reaction up to 300°C.
That is, the weight loss rate is measured between 150° C. and 300° C. in the dynamic TG measurement of a polymer having a lactone ring structure, and the measured weight loss rate obtained is defined as (X). On the other hand, from the composition of the polymer, the theoretical weight loss rate (i.e., 100 (Y) is the weight loss rate calculated assuming that % dealcoholization reaction has occurred.
The theoretical weight loss rate (Y) is, more specifically, the molar ratio of the raw material monomer having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material unit in the polymer composition. It can be calculated from the content of the polymer.
These values (X) and (Y) are calculated according to the dealcoholization formula:
1-(actual weight reduction rate (X)/theoretical weight reduction rate (Y))
, the value is expressed in % to obtain the dealcoholization reaction rate.

The acrylic resin may have atoms or groups derived from components used in polymerization.

For example, the acrylic resin may contain sulfur atoms. In a more specific embodiment, it may have a sulfur-containing group (sulfur-containing skeleton) at least at the terminal of the molecule.

Acrylic resins having such sulfur atoms or sulfur-containing groups can be obtained, for example, by using a thiol compound (for example, a thiol compound described later) as a chain transfer agent.

When the acrylic resin is a copolymer, the form of copolymerization is not particularly limited, and may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like. may

For example, since an acrylic resin has a ring structure, it can usually be said to be a copolymer. and so on.

The melt flow rate (sometimes referred to as M _B ) of the acrylic resin (B) is, for example, 0.1 g/10 min or more (e.g., 0.2 g/10 min or more) at a temperature of 230°C and a load of 3.8 kg. Preferably 0.3 g/10 minutes or more (e.g., 0.4 g/10 minutes or more), more preferably 0.5 g/10 minutes or more (e.g., 0.6 g/10 minutes or more). .7 g/10 minutes or more (eg, 0.8 g/10 minutes or more).

The upper limit of the melt flow rate of the acrylic resin (B) is, for example, 10 g/10 minutes or less, 9.8 g/10 minutes or less, 9.6 g/10 minutes or less, 4 g/10 min or less, 9.2 g/10 min or less, 9 g/10 min or less, 8.8 g/10 min or less, 8.6 g/10 min or less, 8.4 g/10 min or less, 8.2 g/10 min 8 g/10 min or less, 7.8 g/10 min or less, 7.6 g/10 min or less, 7.4 g/10 min or less, 7.2 g/10 min or less, 7 g/10 min or less, etc. good.

A specific range of the melt flow rate of the acrylic resin (B) includes a range combining the above ranges, for example, at a temperature of 230 ° C. and a load of 3.8 kg, 0.1 to 10 g / 10 minutes, 0.3 It may be up to 9 g/10 minutes, 0.5 to 8 g/10 minutes, and the like.

The melt flow rate of the acrylic resin may be measured according to JIS K7210.

The shear viscosity (sometimes referred to as _VB ) of the acrylic resin (B) depends on its type and composition, but at a temperature of 240° C. and a shear rate of 1000/s, it is, for example, 100 to 500 Pa s, preferably 120 to 480 Pa. ·s (for example, 130 to 450 Pa·s), more preferably about 150 to 400 Pa·s.

In addition, the shear viscosity of the acrylic resin may be specifically measured by the method described later.

Excellent melt fluidity (having high melt fluidity) reduces coloring during molding (for example, melt molding such as injection molding), and molded products with low yellowness (melt molded products such as injection molded products) efficiently and easily.

In addition, the high melt fluidity enables molding at a lower temperature, suppresses the heat history in the molding process, thereby reducing the coloring of the molded product, and the time required for the heating and cooling process of the injection device. improvement in productivity can be expected.

A melt flow rate may be selected for each resin combination. For example, the absolute value |M _A −M _B | of the difference between the melt flow rate M _A of the polycarbonate resin (A) and the melt flow rate M _B of the acrylic resin (B) is preferably 50 g/10 min or less, for example. may be 40 g/10 min or less, more preferably 30 g/10 min or less (eg, 28 g/10 min or less, 25 g/10 min or less, 22 g/10 min or less, 20 g/10 min or less).

The shear viscosity may be selected for each resin combination. For example, the absolute value |V _A −V _B | (Pa s) of the difference between the shear viscosity V _A of the polycarbonate resin (A) and the shear viscosity V _B of the acrylic resin (B) is preferably 300 or less, for example. may be 280 or less, more preferably 250 or less (eg, 220 or less, 200 or less, 180 or less, 170 or less, 160 or less).

By preventing the difference in melt flow rate and shear viscosity between the two resins from becoming too large (relatively small), it is easy to stably mix the two resins. It is easy to efficiently obtain a composition (and a compact) (with little variation).

The weight average molecular weight (Mw) of the acrylic resin (B) may be selected from a range of about 5,000 or more (e.g., 7,000 or more), for example, 10,000 or more (e.g., 12,000 or more), preferably 15,000 or more (e.g., 18,000 or more), more preferably 20000 or more (e.g., 25000 or more), 30000 or more (e.g., 35000 or more, 38000 or more, 40000 or more, 42000 or more, 45000 or more, 48000 or more, 50000 or more, 52000 or more, 55000 or more, 58000 or more, 60000 or more, 62000 or more, 65000 or more, etc.).

The upper limit of the weight average molecular weight (Mw) of the acrylic resin (B) may be, for example, 500,000, 400,000, 300,000, 250,000, 200,000, 180,000, 150,000, 120,000.

A specific range of the weight average molecular weight (Mw) of the acrylic resin (B) may be, for example, 20,000 to 200,000, 30,000 to 150,000, 50,000 to 200,000 from the viewpoint of moldability.

The acrylic resin (B) may have a relatively narrow molecular weight distribution (Mw/Mn) from the viewpoint of melt fluidity, strength of the molded product, and the like.
The molecular weight distribution (Mw/Mn) of the acrylic resin (B) is, for example, 1 to 10 (eg, 1.1 to 7.0), preferably 1.2 to 5.0 (eg, 1.5 to 4.0). 0), about 1.5 to 3.0, 2.8 or less, 2.7 or less, 2.6 or less, or 2.5 or less.

The molecular weight (and molecular weight distribution) may be measured by polystyrene conversion using GPC, for example.

Although the acid value of the acrylic resin (B) depends on the application, it is usually preferably small, for example, 10 mmol/g or less, preferably 5 mmol/g or less, more preferably 3 mmol/g or less (eg, 1.5 mmol/g or less). 5 mmol/g or less), or 1.2 mmol/g or less (e.g., 1 mmol/g or less, 0.8 mmol/g or less, 0.7 mmol/g or less, 0.6 mmol/g or less, 0.5 mmol/g). /g or less, 0.4 mmol/g or less, 0.35 mmol/g or less, etc.).

In addition, you may measure an acid value by the below-mentioned method, for example.

The glass transition temperature (Tg) (sometimes referred to as Tg _B ) of the acrylic resin (B) is, for example, 70° C. or higher (eg, 80 to 200° C.), preferably 90° C. or higher (eg, 100 to 180° C.), More preferably, it may be about 110° C. or higher (eg, 112 to 170° C.), may be about 115° C. or higher (eg, 118 to 160° C.), or 120° C. or higher [eg, 120 to 160° C., 125° C. or higher (eg, 126 to 155° C.), 128° C. or higher (eg, 129 to 150° C.)].
The glass transition temperature can be efficiently adjusted by, for example, the content ratio of the ring structure introduced into the acrylic resin. The acrylic resin (B) has a ring structure and often has a relatively high glass transition temperature.

In addition, Tg may be measured, for example, by the method described later.

The glass transition temperature may be selected for each resin combination. For example, the absolute value |Tg _A −Tg _B | of the difference between the glass transition temperature Tg _A of the polycarbonate resin (A) and the glass transition temperature Tg _B of the acrylic resin (B) is, for example, 70° C. or less (for example, 60 C. or lower), preferably 50.degree. C. or lower (eg, 45.degree. C. or lower), more preferably 40.degree.
By keeping the difference in glass transition temperature between the two resins not too large (relatively small), it is possible to efficiently obtain a composition (and a molded product) with relatively uniform (small variation) physical properties (heat resistance, etc.). Cheap.

The refractive index (wavelength 589 nm) (sometimes referred to as R _B ) of the acrylic resin (B) depends on its type and composition (type of ring structure, content ratio), etc. , 1.470 to 1.530), preferably 1.480 to 1.520 (eg, 1.490 to 1.515), more preferably 1.492 to 1.510 (eg, 1.495 to 1.515). 505, 1.496 to 1.502), or 1.494 or more.

The refractive index may be a value at 23° C., and may be measured, for example, by the method described later.

The refractive index may be selected for each resin combination. For example, the absolute value |R _A −R _B | of the difference between the refractive index R _A of the polycarbonate resin (A) and the refractive index R _B of the acrylic resin (B) is, for example, 0.100 or less (eg, 0.100). 090 or less), 0.080 or less (e.g., 0.060 or less), preferably 0.050 or less (e.g., 0.030 or less), more preferably 0.020 or less (e.g., , 0.015 or less, 0.012 or less, 0.010 or less, 0.008 or less, 0.006 or less, 0.005 or less, 0.004 or less, 0.003 or less, 0.0025 or less, 0.002 or less ).
By not increasing the difference in refractive index between the two resins too much (relatively reducing it), the composition (and the molded product) can be easily formed without impairing the transparency or the like.

As the acrylic resin (B), a commercially available product or a manufactured product may be used. A method for producing the acrylic resin (B) will be described below.

(Method for producing acrylic resin)

An acrylic resin (acrylic polymer) can be produced through at least a step of polymerizing a polymerizable component (polymerization step).

The polymerizable component is a monomer that is a raw material for the acrylic resin, and corresponds to the (meth)acrylic acid ester and other monomers exemplified above. The types and preferred embodiments of the monomers are the same as described above.

The acrylic resin has a ring structure, and depending on the type of the ring structure, the polymerizable component may contain a monomer that forms the ring structure or a monomer that serves as a starting material for the ring structure.

For example, when producing an acrylic resin having a structure derived from a maleimide monomer or a maleic anhydride monomer, the polymerizable component is, for example, maleic anhydride, a maleimide-based monomer [e.g., maleimide; N-alkylmaleimide (e.g., N—C _1-10 alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide), N-cycloalkylmaleimides (e.g. N—C _3-20 cycloalkylmaleimides such as cyclohexylmaleimide), N-arylmaleimides (e.g. , N—C _6-10 aryl maleimides such as N-phenyl maleimide), N-substituted maleimides such as N-aralkyl maleimides (e.g., N—C _7-10 aralkyl maleimides such as N-benzyl maleimide), and the like]. You can

When producing an acrylic resin having a lactone ring structure, the polymerizable component is a monomer that is a raw material for the lactone ring, such as 2-(hydroxymethyl)acrylate (e.g., alkyl such as 2-(hydroxymethyl)ethyl acrylate). ester).

When producing an acrylic resin having a lactam ring structure, the polymerization component is a lactam-based monomer [e.g., N-vinylpyrrolidone-based monomer (e.g., N-vinylpyrrolidone, N-vinyl-4-butylpyrrolidone, N -vinyl-4-propylpyrrolidone, N-vinyl-4-ethylpyrrolidone, N-vinyl-4-methylpyrrolidone, N-vinyl-4-methyl-5-ethylpyrrolidone, N-vinyl-4-methyl-5-propyl pyrrolidone, N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-5-propylpyrrolidone, N-vinyl-5-butylpyrrolidone, etc.), N-vinylcaprolactam monomers (e.g., N- vinylcaprolactam, N-vinyl-6-methylcaprolactam, N-vinyl-6-propylcaprolactam, N-vinyl-7-butylcaprolactam, etc.)] and the like.

Polymerization may typically be radical polymerization.

Polymerization may be carried out in the presence of a polymerization initiator (particularly a radical polymerization initiator).

The polymerization initiator (radical polymerization initiator) is not particularly limited. etc.], azo compounds and the like.

Specific polymerization initiators include, for example, organic peroxides [eg, tert-amylperoxyisononanoate, t-amylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5, 5-trimethylhexanate, tert-butyl peroxylaurate, tert-butyl peroxy isopropyl monocarbonate, tert-hexyl peroxy isopropyl monocarbonate, tert-butyl peroxy acetate, 1,1-bis(tert-butyl peroxy ) 3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxy 2-ethylhexanate, tert-butylperoxyisobutyrate, tert-hexylperoxy 2 -ethylhexanate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, etc.], azo compounds [e.g., 2-(carbamoylazo)-isobutyro Nitrile, 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azo bisisobutyrate, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), etc.] and the like.

You may use a polymerization initiator individually or in combination of 2 or more types.

In particular, at least an organic peroxide (peroxyester, etc.) may be suitably used as a polymerization initiator.

The amount (use ratio) of the polymerization initiator used depends on the type of the polymerization initiator, but for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the polymerization component, More preferably, it may be 0.1 parts by mass or more, particularly 0.15 parts by mass or more, and 0.2 parts by mass or more (e.g., 0.25 parts by mass or more, 0.28 parts by mass or more, 0.3 parts by mass or more). parts by mass or more, 0.32 parts by mass or more, 0.35 parts by mass or more, 0.38 parts by mass or more, 0.4 parts by mass or more, 0.42 parts by mass or more, 0.45 parts by mass or more, 0.48 mass parts parts or more, 0.5 parts by mass or more, 0.52 parts by mass or more).

The upper limit of the amount of the polymerization initiator used is not particularly limited, but for example, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight with respect to 100 parts by weight of the polymerization component. , 4.5 parts by mass, 4 parts by mass, 3.5 parts by mass, 3.2 parts by mass, 3 parts by mass, 2.8 parts by mass, 2.5 parts by mass, 2.2 parts by mass, 2 parts by mass, 1 8 parts by weight, 1.5 parts by weight, 1.2 parts by weight, 1 part by weight, 0.9 parts by weight, 0.8 parts by weight, 0.7 parts by weight, and the like.

In particular, the proportion of the polymerization initiator used relative to 100 parts by mass of the polymerization component is relatively large [eg, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more (eg, 0.4 to 0.4 parts by mass). 8 parts by mass), etc.].

By using a relatively large amount of the polymerization initiator in this manner, it is easy to efficiently obtain an acrylic resin that is advantageous in terms of melt fluidity and the like. Moreover, even when a chain transfer agent is used, it is easy to ensure a sufficient polymerization reaction rate, and an acrylic resin having good melt fluidity can be efficiently obtained.

Polymerization may be carried out in the presence of a chain transfer agent.

Examples of chain transfer agents include, but are not limited to, thiol compounds {e.g., primary thiols [e.g., aliphatic primary thiols (e.g., butanethiol, octanethiol, decanethiol, dodecanethiol (n-dodecylmercaptan ), primary alkyl mercaptans such as hexadecanethiol, octadecanethiol, decanetrithiol, preferably primary _C3-30 alkyl mercaptans)], secondary thiols [e.g., aliphatic secondary thiols (e.g., 2-propanethiol, 2-butanethiol, 2-methyl-1-propanethiol, 3-methyl-2-butanethiol, 3-pentanethiol, 2-decanethiol, 3-decanethiol, 4-decanethiol, 5- Secondary alkylmercaptans such as decanethiol, 2-hexadecanethiol, 5-hexadecanethiol, 8-octadecanethiol, preferably secondary _C3-30 alkylmercaptans), alicyclic secondary thiols (e.g., cyclohexanethiol) , cycloalkyl mercaptans such as cyclopentanethiol, preferably C _3-20 cycloalkyl mercaptans), aromatic secondary thiols (e.g., aryl mercaptans such as thiophenol, preferably C _6-20 aryl mercaptans), etc.], Tertiary thiols [e.g., aliphatic tertiary thiols (e.g., tert-alkyl mercaptans such as tert-butyl mercaptan, tert-dodecyl mercaptan, tert-nonyl mercaptan, tert-hexyl mercaptan, preferably C _3-30 tert-alkyl mercaptan), etc.]} and the like.

In addition, when the chain transfer agent contains a polyfunctional thiol, the proportion of the polyfunctional thiol in the chain transfer agent may be small. The amount (percentage of use) of the polyfunctional thiol used in the chain transfer agent is, for example, 20% by mass or less (e.g., 15% by mass or less), preferably 10% by mass or less (e.g., 5% by mass or less), more preferably It may be 3% by mass or less, 1% by mass or less, or 0.5% by mass or less.

One or more chain transfer agents can be used.

The amount (proportion of use) of the chain transfer agent is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and particularly It may be 0.015 parts by mass or more, or may be 0.02 parts by mass or more.

The upper limit of the amount of the chain transfer agent used is not particularly limited, but for example, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1.5 parts by mass, 1 parts by mass, 0.5 parts by mass, 0.25 parts by mass, 0.2 parts by mass, 0.15 parts by mass, 0.1 parts by mass, 0.08 parts by mass, 0.07 parts by mass, etc. .

In particular, even when a chain transfer agent is used, the ratio of the chain transfer agent to 100 parts by mass of the polymerized component is relatively small from the viewpoint of reducing coloring [for example, 0.5 parts by mass or less, 0.1 parts by mass or less ( for example, 0.001 to 0.1 parts by mass)], and a chain transfer agent may not be used.

As described above, even if a chain transfer agent is not used or the amount of the chain transfer agent used is relatively small, it is easy to efficiently obtain an acrylic resin that is advantageous in terms of melt fluidity and the like.

The mass ratio of the chain transfer agent and the polymerization initiator is preferably 1/2 or less, more preferably 1/3 or less, 1/4 or less, or 1/5 from the viewpoint of acrylic resin coloring suppression and melt fluidity. may be: The mass ratio of the chain transfer agent and the polymerization initiator is calculated from (mass of chain transfer agent)/(mass of polymerization initiator).

Polymerization may be carried out in the presence of a polymerization initiator, a chain transfer agent, and other components (for example, a pH adjuster, various catalysts, etc.), if necessary.

Polymerization may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. In particular, solution polymerization may be used from the viewpoint of obtaining a polymer containing no impurities and having stable fluidity. . In solution polymerization, the production of polymers with significantly high molecular weights can be suppressed compared to bulk polymerization, probably because polymerization can be performed relatively uniformly, and it is easy to efficiently obtain polymers having stable fluidity. In addition, as compared with suspension polymerization and emulsion polymerization, impurities such as emulsifiers are not included, so it is easy to efficiently obtain a highly transparent polymer.

When the polymerization is carried out in a solvent (for example, solution polymerization), the solvent can be appropriately selected according to the type of polymerization components, and is not particularly limited. , benzene, toluene, xylene, ethylbenzene, etc.), aliphatic or alicyclic hydrocarbons (e.g., cyclohexane, methylcyclohexane, etc.), halogen-based solvents (e.g., chloroform, methylene chloride, carbon tetrachloride, etc.), etc.], ketones (e.g., acetone, methyl ethyl ketone, etc.), esters (e.g., ethyl acetate, butyl acetate, etc.), ethers [e.g., linear ethers (e.g., diethyl ether, etc.), cyclic ethers (e.g., tetrahydrofuran, dioxane, etc. ), etc.], amides [e.g., N-substituted amides (N-alkyl-substituted alkanamides such as N,N-dimethylformamide)], alcohols (e.g., alkanols such as methanol, ethanol, isopropanol), glycol ethers ( For example, monoalkyl ethers of alkanediols or polyalkanediols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and diethylene glycol monoethyl ether)].

A solvent may be used individually or in combination of 2 or more types.

In the polymerization, the concentration of the polymerization components in the entire polymerization system is, for example, 20% by mass or more (eg, 20 to 70% by mass), preferably 35% by mass or more (eg, 35 to 65% by mass), more preferably 40% by mass or more (eg, 40 to 60% by mass), particularly 45% by mass or more (eg, 45 to 55% by mass).

In addition, each component (for example, polymerization component, polymerization initiator, chain transfer agent, other components, solvent, etc.) may all be present (charged) in the reaction system (reactor) at the stage of polymerization initiation, They may be added (or mixed) as the polymerization progresses, or they may be combined. In such a case, the addition rate and addition time of each component can be appropriately selected.

Each component may be added to the reaction system in multiple portions (two or more times, for example, 2 to 5 times).
In particular, the polymerizable component (monomer) may be added to the reaction system as the polymerization progresses. In this case, the polymerizable component may be added in multiple portions or the polymerized component may be added dropwise. When the polymerizable component is added dropwise to the reaction system, it is easy to obtain an acrylic resin having a relatively narrow molecular weight distribution.
Moreover, a polymerization initiator may be added to the reaction system as the polymerization progresses. In particular, when the polymerization components are added dropwise to the reaction system, the polymerization initiator is also preferably added dropwise to the reaction system. By adding the polymerization initiator to the reaction system as the polymerization progresses, it is expected that safety can be ensured or a polymer with a relatively narrow molecular weight distribution can be obtained.
When adding the polymerization component or the polymerization initiator by dropping, the dropping speed is not particularly limited, but from the viewpoint of easily obtaining an acrylic resin with a relatively small molecular weight, it is preferable to add slowly, for 1 hour or more. (eg, 1 to 10 hours) may be added.

Polymerization is usually carried out at a given temperature (or under heating). The polymerization temperature (reaction temperature) can be appropriately selected according to the type of polymerization component, polymerization initiator, solvent, etc. For example, it is 20° C. or higher, preferably 30° C. or higher (eg, 35 to 180° C.), more preferably 40° C. or higher (eg, 45 to 170° C.), particularly 50° C. or higher (eg, 55 to 160° C.), particularly preferably 60° C. or higher (eg, 65 to 150° C.), usually 70 to 140° C. (eg, 80 to 130° C.).

The polymerization temperature may be changed as the polymerization progresses, but even when it is changed in this way, the polymerization is usually carried out within the above temperature range in many cases.

Polymerization may be carried out under agitation. Also, the polymerization may be carried out in air or under an inert atmosphere (in nitrogen, helium, argon, etc.).

The polymerization time (in the case of aging) can be appropriately selected according to the amount of the polymerized components, the polymerization temperature, etc., and is not particularly limited, but is, for example, 30 minutes or longer (eg, 40 minutes to 24 hours), preferably 1 hour or longer ( For example, 1.5 to 16 hours), more preferably 2 hours or more (eg, 2.5 to 12 hours).

Acrylic resin (B) has a ring structure. Such a ring structure may be formed together with the above-described polymerization depending on the type of ring structure (for example, structures derived from maleimide monomers or maleic anhydride monomers, lactam ring structures, etc. ), after polymerization, it can be formed or introduced into the acrylic resin through a step of forming or introducing a ring structure. A method for forming or introducing a ring structure is not particularly limited, and a known method can be followed.

For example, the lactone ring structure is obtained by cyclizing (cyclization condensation, cyclization treatment, ) can be formed or introduced. Cyclization may be carried out in the presence of a cyclization catalyst [eg, a phosphorus-based catalyst (eg, a phosphate ester such as stearyl phosphate)].

The glutarimide structure can be obtained by a known method such as a method of imidating a (meth)acrylic acid ester unit (for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, JP-A-2006-328334, JP-A-2006-337491, JP-A-2006-337492, JP-A-2006-337493, JP-A-2007-009182, etc. Formed into an acrylic polymer by the method described in) or can be introduced.

The glutaric anhydride structure is formed, for example, by a method of intramolecular dealcoholization between adjacent (meth)acrylic acid ester units and (meth)acrylic acid units (e.g., JP-A-2006-283013, JP-A-2006-335902 It can be formed or introduced into the acrylic polymer by the method described in Japanese Patent Application Laid-Open No. 2006-274118, etc.).

An acrylic resin is obtained through such a polymerization step (and a cyclization step if necessary).

In addition, the resin obtained through the polymerization step may be appropriately purified and separated by a conventional method.

[Other resins]
The composition (molded article) of the present invention may contain other resins, if necessary.

The other resin can be appropriately selected depending on the desired physical properties, application, etc., and is not particularly limited, and may be a thermoplastic resin, a curable resin, or a combination thereof.
You may use another resin individually or in combination of 2 or more types.

Specific other resins include, for example, olefin polymers (eg, polyethylene, polypropylene, ethylene-propylene copolymer, poly(4-methyl-1-pentene), etc.), halogen polymers (eg, polyvinyl chloride , polyvinylidene chloride, vinyl halide polymers such as polyvinyl chloride), styrene polymers [e.g., polystyrene, styrene copolymers (e.g., styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile -Butadiene-styrene block copolymer (ABS resin), acrylate-styrene-acrylonitrile copolymer (ASA resin), etc.)], polyester-based polymers (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.) polyester), polyamide resins (for example, aliphatic polyamide resins such as polyamide 6, polyamide 66, and polyamide 610), polyacetal resins, polyphenylene oxide resins, polyphenylene sulfide resins, polyether ether ketone resins, polysulfone resins , polyethersulfone-based resin, rubbery polymer [e.g., styrene-based resin (e.g., styrene-based copolymer such as ABS resin, ASA resin, etc.) containing rubber (polybutadiene-based rubber, acrylic-based rubber, etc.)], etc. is mentioned.

Other resins also include acrylic resins. Examples of acrylic resins include acrylic resins not belonging to the category of the acrylic resin (B) [e.g., methacrylic esters (e.g., methacrylic esters such as methyl methacrylate and the like)-derived structural units derived from methacrylic resins (e.g., , Polymers with methacrylic acid esters such as polymethyl methacrylate as polymerization components, Polymers with methacrylic acid esters such as methyl methacrylate-styrene copolymer and aromatic vinyl compounds as polymerization components) Acrylics without ring structures such as resin, etc.] and the like.

Other resins also include cellulosic resins. Cellulose resins (cellulose derivatives) include cellulose esters [for example, cellulose acetate (cellulose diacetate, cellulose triacetate), cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acylate such as cellulose acetate butyrate]. ], cellulose ether [e.g., alkyl cellulose (e.g., methyl cellulose, ethyl cellulose, etc.), hydroxyalkyl cellulose (e.g., hydroxyethyl cellulose, hydroxyalkyl cellulose, etc.), carboxyalkyl cellulose (e.g., carboxymethyl cellulose, etc.)], cyanoethyl cellulose, etc. mentioned.

Other resins also include thermoplastic elastomers. The thermoplastic elastomer is not particularly limited, and examples thereof include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, and amide-based elastomers.

Other resins may be selected in combination with each resin. For example, the absolute value of the difference between the refractive index R _C of the other resin and the refractive index R _A of the polycarbonate resin (A) or the refractive index R _B of the acrylic resin (B) |R _A −R _C | or |R _B -R _C | is in the range of, for example, about 0.100 or less (eg, 0.09 or less) from the viewpoint of transparency, although it depends on the compatibility with the resins (A) and/or (B). 0.080 or less (e.g., 0.060 or less), preferably 0.050 or less (e.g., 0.030 or less), more preferably 0.020 or less (e.g., 0.015 or less, 0.012 or less, 0.010 or less, 0.008 or less, 0.006 or less, 0.005 or less, 0.004 or less, 0.003 or less, 0.0025 or less, 0.002 or less) .

[Other ingredients]
The composition (molded article) of the present invention may contain other components, if necessary.
Such other components can be selected depending on the desired use, physical properties, etc., and may contain other components (additives). Other components (additives that are not colorants) are not particularly limited, and examples include ultraviolet absorbers, colorants, antioxidants (e.g., phenolic antioxidants, thioether antioxidants, phosphoric acid antioxidants, agents, etc.), stabilizers, reinforcing materials, flame retardants, antistatic agents, organic fillers, inorganic fillers, antiblocking agents, resin modifiers, organic fillers, inorganic fillers, plasticizers, lubricants, matting agents (e.g. , inorganic compound particles such as silica and titanium oxide, glassy polymer particles such as polymethyl methacrylate and polystyrene), retardation reducing agents, and the like.

You may use another component individually or in combination of 2 or more types.

The ultraviolet absorption ability of the ultraviolet absorber (UVA) may be in the wavelength range of 300 to 380 nm, and the molar extinction coefficient (chloroform solution) for light of the wavelength at which the absorption by UVA is maximum is 10000 (L · mol ⁻¹ ·cm ⁻¹ ) or more.

Examples of ultraviolet absorbers (UVA) include, but are not limited to, benzophenone compounds, salicicate compounds, benzoate compounds, triazole compounds, and triazine compounds.

Triazole compounds include, for example, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(3, 5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, 2-benzotriazol-2-yl-4,6-di-t-butylphenol, 2-[5-chloro(2H)-benzotriazole-2 -yl]-4-methyl-6-(t-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-butylphenol, 2-(2H-benzotriazole-2- yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthal imidylmethyl)phenol, reaction product of methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 2-(2H- benzotriazol-2-yl)-6-(linear and branched dodecyl)-4-methylphenol, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5- Bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-C _7-9 side chain and straight chain alkyl esters, and the like. A triazole compound having a halogen atom, such as a chlorine atom, is preferred because of its high ultraviolet absorption ability.

Triazine compounds include, for example, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxy phenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxy phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy -4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl- 6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyethoxy)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4- dibutoxyphenyl)-1,3-5-triazine, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, 2,4-bis( 2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-alkyloxy-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine skeleton (alkyloxy; octyloxy, nonyloxy, and UVA having a long-chain alkyloxy group such as decyloxy). Among them, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-alkyloxy-2-hydroxypropyloxy)-5 has excellent ultraviolet absorption performance. -α-cumylphenyl]-s-triazine skeleton (alkyloxy; long-chain alkyloxy groups such as octyloxy, nonyloxy and decyloxy) is preferred.

Although the molecular weight of UVA is not particularly limited, it is preferably 600 or more. The upper limit of the molecular weight of UVA may be, for example, 10,000, 8,000, 5,000, and the like.

You may use an ultraviolet absorber individually or in combination of 2 or more types.

The coloring agent is not particularly limited, and can be appropriately selected depending on the application of the composition, and may be, for example, a pigment (eg, inorganic pigment, organic pigment), dye, or the like.

In addition, the colorant may have a bluing property [property of correcting (negating) and suppressing the color (eg, yellow) of the acrylic resin or composition].
Such a coloring agent may be a coloring agent (compound) having a maximum absorption wavelength of 520 to 600 nm, 540 to 580 nm, etc., depending on the color to be corrected.

Such coloring agents can be appropriately selected according to the type (wavelength) of the color to be corrected, and examples include compounds having an anthraquinone skeleton (anthrachitone compounds), compounds having a phthalocyanine skeleton (phthalocyanine compounds), Examples include compounds having an azo skeleton (azo compounds), compounds having a triarylmethane skeleton (triarylmethane compounds), and the like.
Among these, compounds having an anthraquinone skeleton may be preferably used from the viewpoint of heat resistance.

Specific coloring agents (coloring agents having bluing properties, bluing agents) include anthraquinone-based dyes [for example, Solvent Violet 13 (CA. No (color index number) 60725), Solvent Violet 14, Solvent Violet 31 (CA. No68210), Solvent Violet33 (CA.No60725), Solvent Violet36 (CA.No68210), Solvent Blue45 (CA.No61110), Solvent Blue94 (CA.No61500), Solvent Blue87, Solvent Blue97, D isverse Violet 28 etc.], phthalocyanine dyes [ Examples thereof include Solvent Blue 25 (CA. No. 74350), etc.], monoazo dyes [eg, Solvent Violet 21, etc.], triarylmethane dyes [eg, Solvent Blue 2 (CA. No. 42563), etc.].

Examples of such colorants include commercially available products such as "Macrolex (registered trademark) Violet B", "Macrolex (registered trademark) Violet 3R", and "Macrolex (registered trademark) Blue RR" (manufactured by Lanxess Corporation). ), “Sumiplast (registered trademark) Violet B”, “Sumiplast (registered trademark) Green G” (manufactured by Sumika Chemtex Co., Ltd.), “Polysynthrene (registered trademark) Blue RLS” (manufactured by Clariant), “Diaresin Violet D” , "Diaresin Blue G", "Diaresin Blue N" (manufactured by Mitsubishi Chemical Corporation), etc. may also be used.

You may use a coloring agent individually or in combination of 2 or more types.

[Composition and molding]
In the composition (molded article), the ratio of the polycarbonate resin (A) or the acrylic resin (B) (the ratio of either one of the polycarbonate resin (A) and the acrylic resin (B)) is (or resin component), for example, can be selected from a range of 0.1% by mass or more (e.g., 0.1 to 99.9% by mass), 0.3% by mass or more (e.g., 0.5% by mass) % or more), preferably 1% by mass or more (e.g., 2% by mass or more, 3% by mass or more, 4% by mass or more), more preferably 5% by mass or more (e.g., 6% by mass or more, 7% by mass or more, 8% by mass or more, % by mass, 9% by mass or more, 10% by mass or more), etc., and 12% by mass or more (e.g., 15% by mass or more, 18% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass) % or more, 35 mass % or more, 40 mass % or more, 45 mass % or more, 50 mass % or more, 50 mass % or more, 51 mass % or more, etc.).

The composition (molded article) may contain either the polycarbonate resin (A) or the acrylic resin (B) in a predetermined proportion (in some cases, in a relatively large amount).
In the composition (molded article) of the present invention, the physical properties including transparency and the like can be realized as described above regardless of the mixing ratio of the polycarbonate resin (A) or the acrylic resin (B). The physical properties (desired physical properties) of the composition (or molded article) can be efficiently adjusted according to the mixing ratio of the above.
For example, in a composition (or molded article) containing a relatively large amount of either one of the polycarbonate resin (A) and the acrylic resin (B), while maintaining the physical properties derived from one resin without impairing the other resin, The physical properties derived from the resin can be efficiently realized or imparted.
In such a composition (molded article), the ratio of the polycarbonate resin (A) or the acrylic resin (B) (the ratio of either one of the polycarbonate resin (A) and the acrylic resin (B)) is , With respect to the total amount of the polycarbonate resin (A) and the acrylic resin (B), for example, 1% by mass or more, preferably 3% by mass or more (e.g., 5% by mass or more, 10% by mass or more, 15% by mass or more ) may be about 20% by mass or more (e.g., 25% by mass or more), 30% by mass or more (e.g., 40% by mass or more, 45% by mass or more, 50% by mass or more, 50% by mass or more, 51% by mass or more , 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more).

In such a composition (molded article), the ratio of the polycarbonate resin (A) or the acrylic resin (B) (the ratio of either one of the polycarbonate resin (A) and the acrylic resin (B)) The upper limit of the ratio) is not particularly limited, but is, for example, 99.9% by mass or less, 99.7% by mass or less (e.g., 99 .5 mass% or less), preferably 99 mass% or less (e.g., 98 mass% or more, 97 mass% or less, 96 mass% or less), more preferably 95 mass% or less (e.g., 94 mass% or less, 93 mass% hereinafter, 92% by mass or less, 91% by mass or less, 90% by mass or less), etc., and 88% by mass or less (e.g., 85% by mass or less, 82% by mass or less, 80% by mass or less, 75% by mass or less) , 70% by mass or less, etc.).

Such a composition (molded article) [a composition (molded article) containing either one of the polycarbonate resin (A) and the acrylic resin (B) in a predetermined proportion (in some cases, containing a relatively large amount) ], the ratio of the other of the polycarbonate resin (A) and the acrylic resin (B) is 99% by mass or less, 95% by mass, with respect to the total amount of the polycarbonate resin (A) and the acrylic resin (B) % or less (e.g., 93% by mass or less), preferably 90% by mass or less (e.g., 85% by mass or more, 80% by mass or less, 75% by mass or less), more preferably 70% by mass or less (e.g., 65% by mass or less , 60% by mass or less, 55% by mass or less, 55% by mass or less, 50% by mass or less), etc., and less than 50% by mass (e.g., 49% by mass or less, 48% by mass or less, 47% by mass or less, 46% by mass or less, 45% by mass or less, 42% by mass or less, 40% by mass or less, 38% by mass or less, 35% by mass or less, 32% by mass or less, 30% by mass or less, etc.).
In addition, such a composition (molded body) [composition (molding Body)], the ratio of the other of the polycarbonate resin (A) and the acrylic resin (B) (the lower limit of the ratio) is relative to the total amount of the polycarbonate resin (A) and the acrylic resin (B) , 0.1% by mass or more (e.g., 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 7 % by mass, 8% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more).

In the composition (molded article), the mass ratio of the polycarbonate resin (A) and the acrylic resin (B) (former/latter (mass ratio)) is, for example, 0.1/99.9 to 99.9/0. It may be selected from a range of about 1, 0.5/99.5 to 99.5/0.5, preferably 1/99 to 99/1 (eg, 2/98 to 98/2), more preferably may be about 3/97 to 97/3 (eg, 4/96 to 96/4), 5/95 to 95/5 (eg, 6/94 to 94/6, 7/93 to 93/ 7, 2/98 to 98/2, 9/91 to 91/9, 10/90 to 90/10).

Also, as in the above, a composition (molded article) containing either one of the polycarbonate resin (A) and the acrylic resin (B) in a predetermined proportion may be used.
In such a composition (molded article), the mass ratio of one resin to the other resin (former/latter (mass ratio)) is, for example, 1/99 to 99.9/0.1 (for example, 3 /97 to 99.5/0.5), 5/95 to 99/1, preferably 10/90 to 98/2 (eg, 20/80 to 97/3), and further Preferably it may be about 30/70 to 97/3 (eg, 35/65 to 96/4), 40/60 to 99/1 (eg, 45/55 to 98/2, 50/50 to 90 /10, 51/49 to 97/3).

When the composition (molded article) contains other resins, the content of the other resins is the total amount of the composition [or the resin component (polycarbonate resin (A), acrylic resin (B) and other resins). On the other hand, for example, it can be selected from a range of about 70% by mass or less (eg, 0.1 to 60% by mass), 50% by mass or less (eg, 0.5 to 40% by mass), preferably 30% by mass or less ( For example, it may be about 1 to 25% by mass), 20% by mass or less (eg, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, 1 to 10% by mass, etc.) may be

In addition, from the viewpoint of efficiently expressing the physical properties of the combination of the polycarbonate resin (A) and the acrylic resin (B), even when other resins are contained, other resins (especially other non-acrylic resins) It is preferred that the proportion is not too large.

When the composition contains other components (additives), the ratio of the other components is, for example, about 0.01 to 10% by mass (eg, 0.05 to 5% by mass) with respect to the entire composition. may be

In the composition (further, the molded article), the existence form (mixed form) of the polycarbonate resin (A) and the acrylic resin (B) is not particularly limited, but may be mutually compatible or incompatible. good too.
The presence or absence of compatibility may be confirmed by, for example, thermal analysis (DSC).

Further, the composition may be a melt-blended (melt-kneaded) mixture (melt mixture) or a non-melt-blended (melt-kneaded) mixture (dry blend).

As described below, the composition of the present invention can be subjected to molding without melt-mixing (melt-kneading). Even if the resins are not compatible with each other, and even if the two resins are not melt-mixed, the composition can be formed and the desired physical properties can be efficiently exhibited.

In particular, by using a composition that does not melt and mix (and is in an incompatible state), the heat history up to molding can be reduced as much as possible. easy to obtain.

The composition (resin composition) of the present invention may generally be thermoplastic (thermoplastic resin composition).

The total light transmittance of the composition (molded article) may be relatively high, for example, 88% or more (e.g., 88.5% or more), preferably 89%, depending on its constituent components. or more (eg, 89.5% or more), more preferably 90% or more (eg, 90.5% or more, 91% or more).

In addition, the upper limit of the total light transmittance may be 100%, and may be, for example, 99.9%, 99%, 98%, 97%, 96%, 95%.

The haze of the composition (molded article) may be relatively high, for example, 35% or less (e.g., 30% or less), preferably 25% or less (e.g., 20% or less), although it depends on its constituent components. % or less), more preferably 15% or less (e.g., 12% or less, 10% or less, 8% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less) good too.

The lower limit of haze may be 0% (or detection limit), for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%. may

The total light transmittance and haze are determined, for example, by a predetermined thickness [e.g., a thickness of 3 mm or 500 μm {e.g., a film or sheet with a thickness of 3 mm or 500 μm [film or sheet-like molded product (melt molding such as extrusion molding, injection molding, etc. Body, etc.)] etc.] etc.] [for example, a value measured in accordance with JIS K7361 using a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH 5000)]. may be a value measured by the method described later.

The yellowness index (YI) of the composition (molded article) may be relatively small, for example, 4 or less, preferably 3.5 or less, more preferably 3 or less, depending on its constituent components. 2.8 or less, 2.6 or less, 2.5 or less, 2.4 or less, 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, 1.9 or less, It may be 1.8 or less.

In addition, the lower limit of yellowness may be 0 (or detection limit), and a finite value (for example, 0.01, 0.02, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, etc.).

The degree of yellowness is determined, for example, by a predetermined thickness [e.g., a thickness of 3 mm, 75 µm, 50 µm, etc. {e.g., a film or sheet of a thickness of 3 mm, 75 µm, 50 µm, etc. Melt molding etc.)] etc.] etc.] value [for example, using a spectrophotometer (Shimadzu Corporation, UV-3600), C2 degree light source, wavelength range of 380 nm to 780 nm, in accordance with the provisions of JIS K7373 It may be a value measured by the method described later.

The b ^* value of the composition (molded body) may be relatively small, for example, 1 or less, preferably 0.9 or less, more preferably 0.8 or less, depending on its constituent components. 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.15 or less, or 0.1 or less.

Note that the lower limit of the b ^* value may be 0 (or the detection limit) or a finite value (eg, 0.01, 0.02, 0.05, etc.).

The b ^* value is, for example, a film or sheet having a thickness of 3 mm, 75 μm, 50 μm, etc. {for example, a thickness of 3 mm, 75 μm, 50 μm, etc. (Molten molded product, etc.)] etc.] etc.] [For example, a value measured in accordance with the provisions of JIS Z 8729 using a spectral color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., Colormeter ZE6000)] It may be a value measured by a method described later in detail.

The pencil hardness of the composition (molded body) may be, for example, H or higher (eg, 2H or higher), depending on its constituent components.

The pencil hardness is, for example, a film or sheet having a thickness of 3 mm, 75 μm, 50 μm, etc. [e.g., a thickness of 3 mm, 75 μm, 50 μm, etc.] Molten molded product etc.)] etc.] etc.] value [for example, using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) at a load of 750 g, Measured in accordance with the provisions of JIS K5600-5-4: 1999 measured value], or more specifically, it may be a value measured by a method described later.

The Martens hardness of the composition (molded body) depends on its constituent components, but is, for example, 100 N/mm ² or more (eg, 105 to 250 N/mm ² ), preferably 110 N/mm ² or more (eg, 115 to 250 N/mm 2 ) or more. 220 N/mm ² ), more preferably 120 N/mm ² or more (eg, 125 N/mm ² or more, 130 N/mm ² or more, 135 N/mm ² or more, 132 to 200 N/mm ² , etc.).

Martens hardness is determined, for example, by a film or sheet [film or sheet-like molded product (extrusion molded product, injection molded product, etc. Melt molded product etc.)] etc.] etc.] value [for example, using an ultra-micro hardness tester (manufactured by Fisher Instruments Co., Fischer Scope HM-2000), measured in accordance with the provisions of ISO-14577-1 value], or more specifically, it may be a value measured by a method described later.

The elastic modulus of the composition (molded body) depends on its constituent components, but is, for example, 0.5 GPa or more (eg, 0.7 to 20 GPa), preferably 1 GPa or more (eg, 1.5 to 15 GPa), and further Preferably, it may be about 2 GPa or more (eg, 3 to 10 GPa).

The tensile strength of the composition (molded article) depends on its constituent components, but is, for example, 10 MPa or higher (eg, 20 to 300 MPa), preferably 30 MPa or higher (eg, 40 to 200 MPa), more preferably 50 MPa or higher (eg, , 50 to 150 MPa, 60 to 120 MPa, 70 to 100 MPa).

The elongation at break of the composition (molded article) depends on its constituent components, but is, for example, 10% or more (eg, 20 to 100%), preferably 30% or more (eg, 35 to 95%), more preferably It may be about 40% or more (eg, 45% or more, 55% or more, 60% or more, 60-90%, 65-85%, 70-90%).

The modulus, tensile strength, and elongation at break may be in a particular direction (eg, MD and/or TD).

The elastic modulus, tensile strength, and elongation at break can be measured according to JIS K 7127:1999 using, for example, Autograph (AGS-X, manufactured by Shimadzu Corporation). Specifically, it may be performed under the conditions of a test speed of 5 mm / min and a gauge distance of 25 mm, and a predetermined thickness [e.g., a thickness of 75 μm, 50 μm, etc. {e.g., a film or sheet [film or It may be a value in a sheet-like molded article (eg, stretched film)], etc.), or more specifically, it may be a value measured by the method described later.

The folding endurance (MIT) of the composition (molded article) depends on its constituent components, but is, for example, 10 times or more (eg, 30 to 3000 times), preferably 50 times or more (eg, 80 times or more, 80 times or more). up to 1000 times), more preferably 100 times or more (eg, 120 times or more, 150 times or more, 180 times or more, 200 times or more, 250 times or more, 100 to 500 times, etc.).
The MIT may be in a particular direction (eg, MD and/or TD).

The number of folding endurance can be measured according to JIS P8115, for example, using an MIT folding endurance tester (manufactured by Toyo Seiki, model DA). Specifically, it may be performed under the conditions of a bending angle of 135°, a bending speed of 175 cpm, and a load of 200 g. It may be a value in a sheet-like molded article (eg, stretched film)], etc.), or more specifically, it may be a value measured by the method described later.

The tear strength (trouser tear strength) of the composition (molded article) depends on its constituent components, but is, for example, 5 mN or more (eg, 10 to 500 mN), preferably 20 mN or more (eg, 25 to 400 mN), more preferably. may be about 30 mN or more (eg, 35 to 300 mN, 40 to 250 mN, 50 mN or more, 52 mN or more, 50 to 200 mN).
Tear strength may be in a particular direction (eg, MD and/or TD).

The tear strength can be measured according to JIS 7128-1:1998 using, for example, Autograph (AGS-X, manufactured by Shimadzu Corporation). Specifically, it may be performed at a test speed of 200 mm / min, and a predetermined thickness [e.g., a thickness of 75 μm, 50 μm, etc. {e.g., a film or sheet of a thickness of 75 μm, 50 μm, etc. [film or sheet-shaped molded body (e.g., Stretched film)], etc.], etc.], or more specifically, it may be a value measured by the method described later.

The impact strength (film impact strength) of the composition (molded article) depends on its constituent components, but is, for example, 0.01 J or more (for example, 0.03 to 5 J), preferably 0.05 J or more (for example, 0 .1 to 2 J), more preferably 0.15 J or more (for example, 0.18 to 1 J, 0.2 to 0.5 J, 0.2 J or more, 0.22 J or more, 0.25 J or more). good.

The impact strength can be measured according to ASTM D3420 using, for example, a film impact tester (manufactured by Tester Sangyo Co., Ltd., product number: BU-302). Specifically, it may be performed in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and a predetermined thickness [for example, a film or sheet having a thickness of 75 μm, 50 μm, etc. It may be a value in a molded article (eg, stretched film)], etc.), or more specifically, it may be a value measured by the method described later.

The heat shrinkage of the composition (molded article) depends on its constituent components, but is, for example, 3% or less (eg, detection limit ~ 2%), preferably 1.5% or less (eg, 0.01 to 1 .2%), more preferably about 1% or less (eg, 0.05 to 0.8%, 0.5% or less, 0.3% or less, 0.2% or less).
Heat shrinkage may be in a particular direction (eg, MD and/or TD).
The heat shrinkage rate may be, for example, a value after holding at 100° C. for 1 hour, and a predetermined thickness [for example, a film or sheet having a thickness of 75 μm, 50 μm, etc. It may be a value in a molded article (eg, stretched film)], etc.), or more specifically, it may be a value measured by the method described later.

The photoelastic coefficient (×10 ⁻¹² /Pa) (or its absolute value) of the composition (molding) is, for example, 30 or less (eg, 28 or less), preferably 27 or less, although it depends on its constituent components. More preferably, it may be 26 or less (eg, 25 or less, 22 or less, 20 or less, 18 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less).

The photoelastic coefficient may be, for example, a value in a film having a thickness of 100 mm {for example, a film having a thickness of 100 mm (unstretched film, sheet), etc.}, and more specifically, may be a value measured by the method described later. .

The physical properties of the composition (molded article) as described above can be adjusted by selecting the composition of each resin.

The composition of the present invention can usually be produced by mixing each component (at least the polycarbonate resin (A) and the acrylic resin (B)). The mixing method is not particularly limited, and may be melt mixing (melt kneading) or non-melt mixing (dry blending, etc.). may be non-melt mixed.

Such mixing can also be performed during molding (or during molding, eg, in a molding machine). For example, each resin may be fed into a hopper of a molding machine in a predetermined ratio from two constant feeders and blended in the molding machine (at the time of molding).

When the composition contains other resins, the mixing of the other resins may be either melt-mixing or non-melt-mixing.

Such other resins may be mixed at the same time as polycarbonate resin (A) and acrylic resin (B) are mixed, and may be mixed (melted) in at least one of these resins (for example, acrylic resin (B)) in advance. mixing, non-melt mixing).
In particular, when the other resin is compatible with either the resin (A) or the acrylic resin (B) but is not compatible (difficult) with the other resin or has a large difference in refractive index, etc. In, one resin may be previously melt-mixed with another resin. On the other hand, as long as the resin has a small difference in refractive index, it may be mixed simultaneously or without melting.

The present invention includes a molded article (molded article) containing (formed from) the composition.

The shape of such a molded body is not particularly limited, and may be a two-dimensional shape [eg, film (or sheet), etc.], a three-dimensional shape (eg, block shape, etc.), or the like.

In addition, the film (or sheet) may be in a shape (for example, roll shape) before being formed into various molded products.

The film (or sheet) may be either an unstretched film or a stretched film depending on its use and desired physical properties (strength). From the viewpoint of strength, etc., it may be a stretched film (sheet).
The stretched film may be, for example, a uniaxially stretched film, a biaxially stretched film, or the like.

In the stretched film, the draw ratio (e.g., uniaxial draw ratio, each draw ratio in the MD direction and the TD direction) is not particularly limited, but is, for example, 1.01 times or more (e.g., 1.05 or more, 1.1 or more). , 1.2 or more, 1.3 or more, 1.5 or more, etc., or 5 or less (eg, 4 or less, 3.5 or less, 3 or less, etc.).

The thickness of the film (or sheet) can be appropriately selected according to the resin composition (for example, which of the polycarbonate resin (A) and the acrylic resin (B) is included more) and the application. (e.g., 5 μm or more), preferably 10 μm or more (e.g., 20 μm or more), more preferably 30 μm or more (e.g., 40 μm or more, 50 μm or more, 80 μm or more, 100 μm or more, 120 μm or more, 150 μm or more, 200 μm or more, 300 μm or more, etc. ), or 10 mm or less (eg, 5 mm or less, 3 mm or less, 2 mm or less, 1 mm or less, 800 μm or less, 500 μm or less, 300 μm or less, etc.).

The molded article (molded article) may have physical properties similar to those of the composition. Such physical property values can be selected from the same range as described above.

The method for producing the molded article (molding method) can be selected depending on the form of the molded article, and known molding methods (e.g., extrusion molding, injection molding, cast molding, blow molding, foam molding, casting method, etc.) can be used. The molding may be molding accompanied by decoration (decorative molding, in-mold molding).

In particular, according to the composition of the present invention, it is possible to provide a molded article having the physical properties as described above even after melt molding (injection molding, etc.).

Thus, the molded body may in particular be a melt molded body [extrusion molded body, injection molded body (injection molded article)].

Molded articles can be applied to various uses, but because they often have excellent transparency (and low colorability) and excellent optical properties due to the composition, they are suitable for optical applications, for example. may also be (may be an optical member).

Examples of specific applications include light guide members, film applications [e.g., protective films (optical protective films, etc.), optical films (optical sheets), etc.], lenses (optical lenses, etc.), covers (lens covers, etc.), foam (foam molding) applications (e.g. cushioning materials, heat and heat insulation materials, damping materials, soundproofing materials, sealing materials, packing materials, etc.), interior and exterior material applications [e.g., in front of in-vehicle displays Interior and exterior material applications for vehicles (automobiles, etc.) such as face plates, meter covers, etc.].

Examples of lenses (optical lenses, etc.) include Fresnel lenses, linear Fresnel lenses, lenticular lenses, plane prisms, fly-eye lenses, aspherical lenses, condenser lenses, microlenses, collimator lenses, concave lenses, convex lenses, diffractive lenses, and the like. mentioned.
Applications of lenses (lens members) include, for example, head-up displays, cameras (for example, in-vehicle cameras), and LIDAR devices. Examples of lenses for such applications include Fresnel lenses and condenser lenses used in head-up displays, and Fresnel lenses, condenser lenses, collimator lenses, and convex lenses used in LIDAR devices.

Examples of light guide members include light guide members [or lamps such as lamps or lights]. The light guide may be for automobiles, motorcycles, or the like. The part (or application) where the light guide is provided is not particularly limited.

Specific members (light guide members) include light covers and light guides {light guides for vehicle lamps [for example, light guides for automobile headlamps (for example, light guides for DRL, etc.)]} and the like.

Examples of protective films include protective films for substrates of various optical discs (VD, CD, DVD, MD, LD, etc.), polarizer protective films used for polarizing plates for liquid crystal display devices, and the like.

Examples of optical films (optical sheets) include retardation film, zero retardation film (in-plane and thickness direction retardation is infinitely small), viewing angle compensation film, light diffusion film, reflective film, antireflection film, anti-reflection film, Glare films, brightness enhancement films, conductive films for touch panels, diffusion plates, light guides, retardation plates, zero retardation plates, prism sheets, and the like.

Among them, the composition of the present invention can be applied to melt molding methods such as extrusion molding and injection molding as described above, so that the molded body can be a two-dimensional shaped body (film or sheet) or a three-dimensional It may also be a shaped body.

In particular, molded articles for optical use (optical members) may require high transparency (furthermore, low colorability, high surface hardness, etc.), and the composition of the present invention is suitable for such molded articles. can be preferably configured.

The shaped article [for example, film (sheet)] of the present invention may be a decorated shaped article [decorated film (sheet), etc.]. In such a decorated molded article, the composition of the present invention may constitute the whole or a part thereof.

For example, the decorated molded article (film) may have a multi-layered structure, even if some or all of the layers are composed of layers (film) formed from the composition of the present invention. good. An example of such a molded article decorated with a multilayer structure is, for example, a molded article having at least a hard coat layer and a substrate layer (base film), wherein at least the base film is the composition of the present invention. Examples include a molded body formed by Such a mode of use of the composition of the present invention can also be said to be a composition for a decorated molded article (decorated film).

In such a decorated molded article, excellent strength may be required for molding, etc., but the composition of the present invention realizes excellent strength that can withstand such molding. Therefore, such a decorative film can be efficiently formed. Such a decorated molded body may be further applied to a plate (steel plate, resin plate) or the like to form (constitute) a molded body (decorative molded body, for example, a vehicle member, etc.).

An example of the decorative film (decorated molded article) and the decorated molded article will be described below.

<Decorative film>
The decorative film may be, for example, a laminate (molded article having a multilayer structure) including a hard coat layer and a substrate layer.

The base material layer usually plays a role of supporting the hard coat layer, other colored layers, adhesive layers, and the like, which will be described later.
The substrate layer (base film) is not particularly limited as long as it is a film that plays a role as a support, and known ones can be used. For example, polyethylene film, polypropylene film, polyester film, polycarbonate film, polymethyl methacrylate film, polyamide film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polystyrene film, polyacrylonitrile film, aluminum foil, paper etc., and one or more of them can be laminated.

In particular, polyester film, polycarbonate film, polymethyl methacrylate film, polyethylene, and polypropylene are preferred from the viewpoint of transparency and moldability. These films can be used alone or in combination of multiple types. For example, a PMMA/PC film in which polymethyl methacrylate (PMMA) is co-extruded on polycarbonate (PC), a polycarbonate A film obtained by laminating a film and a polyester film with an adhesive may also be used.
Polycarbonate film has good moldability, polyester film has good solvent resistance (for organic solvents, sunscreen creams, etc.), and polymethyl methacrylate film has good hardness. The combination can be appropriately selected and used.

As described above, the composition of the present invention may constitute at least a part of the decorative film, and in particular, it may constitute at least a substrate layer (base film).
Such a substrate layer (base film) may be composed (formed) of the composition of the present invention alone, and may be composed of a layer composed (formed) of the composition of the present invention and a composition of the present invention. It may be configured (formed) with other layers that are not covered. Other layers include the films exemplified above.

A peelable film may be laminated as a protective film on the non-facing side of the base material layer that does not face the hard coat layer. In particular, polycarbonate-based substrates are easily scratched, so it is preferable to protect the back side with a protective film until just before use.

The thickness of the substrate layer is not particularly limited, but from the viewpoint of moldability and durability, it is preferably 5 to 1000 μm, more preferably 10 to 500 μm, further preferably 10 to 400 μm. preferable. The base material layer may be a combination of a plurality of types of base materials having different thicknesses, in which case the total thickness of the combined base material layers is preferably 5 to 1000 μm.

The hard coat layer is formed, for example, from a cured product (for example, a thermoset product obtained by thermal curing) of a curable composition (a curable composition for forming a hard coat layer).

A curable composition usually contains a curable resin. The curable resin is not particularly limited, and may be a thermosetting resin, a photocurable resin, or the like. Typically, an acrylic resin (a heat- or photo-curable acrylic resin) may be suitably used.

The curable composition may contain a curing agent (for example, an isocyanate compound, etc.) depending on the type of curable resin. In addition, the curable composition may contain a solvent (diluent) and the like as appropriate.
As such a curable composition (curable resin, curing agent, etc.), known or commonly used ones may be used (eg, those described in JP-A-2019-119049, etc.).

A method for providing the hard coat layer on the base material layer will be described. The hard coat layer can be provided, for example, by coating and curing the curable composition described above on one side of the substrate layer. More specifically, the curable composition described above is applied to the substrate layer and, if necessary, immediately placed in a drying oven to volatilize the solvent. Furthermore, if necessary, after the solvent evaporates, aging is performed to react the curable resin {for example, react the curable resin [for example, acrylic resin (heat or light) having a functional group (hydroxyl group, carboxyl group, etc.) The hard coat layer can be obtained by reacting (curing) the functional group of the curable resin) with the functional group in the curing agent.

Alternatively, the hard coat layer can be provided on the substrate layer using an adhesive.
Specifically, the curable composition is applied onto a release sheet, and if necessary, placed in a drying oven to volatilize the solvent. Furthermore, if necessary, after the solvent evaporates, aging is performed to react the curable resin {for example, react the curable resin [for example, acrylic resin (heat or light) having a functional group (hydroxyl group, carboxyl group, etc.) A cured coating film (cast film) is obtained by reacting the functional group of the curable resin) with the functional group in the curing agent. Next, a lamination adhesive is applied to the cast film and/or the base layer, and if the lamination adhesive contains a solvent, the solvent is volatilized, and then the cast film and the base layer are laminated to form a hard coat layer. and a base layer can be obtained. The peelable sheet is appropriately peeled off before and after lamination.

As a method for applying the curable composition, known methods can be used, and specific examples include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like.

When drying the curable composition, the curable composition is preferably dried at 50 to 200°C, more preferably at 70 to 120°C. Furthermore, the oven is divided into several zones, for example, the first zone is 50 ° C., the second zone is 70 ° C., the third zone is 100 ° C., etc., so that the oven temperature is ramped from low to high. It is preferable to set The residence time in the oven is usually about 1 to 10 minutes. A method of preparing several ovens with fixed temperatures and drying for several minutes in each oven at each temperature may also be adopted.

After drying, depending on the type of curable composition, etc., the curable resin reacts {for example, the curable resin reacts [for example, a functional group (hydroxyl group , a carboxyl group, etc.) and a functional group in the curing agent] etc.) proceeds (aging). In addition, a method can also be selected in which the temperature of the oven is increased to about 100 to 200° C. in the drying step described above, and the reaction is completed while the material is passing through the oven.

The solvent is dried in an oven, and the laminated body taken out may be aged as a sheet, or may be aged as it is wound into a roll. In either case, tackiness remains in the coating film before aging, and blocking may occur when the film overlaps the opposite side of the substrate layer. In order to prevent such a blocking phenomenon, a separator for blocking prevention can be laminated on the coating film when stacking the sheets or when winding them into a roll. As the separator, a PET film subjected to a release treatment, an unstretched propylene film, a polyethylene film, or the like is preferably used.

The curable composition is preferably defoamed before being applied to the substrate layer or the release sheet. If bubbles are contained in the curable composition, bubbles will be mixed in the coating film being formed when the base layer or the release sheet is coated, and bubbles will appear on the surface of the coating film after drying or curing. may leave crack marks. As a method for defoaming, it is possible to wait until bubbles disappear after stirring, or forcibly defoaming using a vacuum deaerator or the like.

The decorative film can be further provided with other layers such as an adhesive layer and a colored layer as described later. The adhesive layer can be provided between the hard coat layer and the base material layer and used to bond the hard coat layer and the base material layer together. Alternatively, when using a plurality of base layers or when using a colored layer, it is also used for laminating various layers.
An adhesive layer may be provided on the side opposite to the hard coat layer side of the base material layer, and the decorative film and an object to be decorated such as a molded object may be pasted together.

Adhesives constituting the adhesive layer are not particularly limited, and known ones can be used. The above can be used in combination.
Components constituting these adhesives are not particularly limited, and examples include polyester resins, poly(meth)acrylate resins, polyurethane resins, polyether resins, polyamide resins, polyimide resins, polyethylene resins, polystyrene resins, polypropylene resins, and ethylene-acetic acid. Vinyl resins, polyvinyl alcohol resins, epoxy resins, silicone resins, phenol resins, styrene-butadiene rubbers, nitrile rubbers, natural rubbers, etc., can be used alone or in combination of two or more.

A method for providing an adhesive layer will be described. The adhesive layer can be formed by directly coating and drying an adhesive containing a solvent on the base material layer or hard coat layer, or by softening an adhesive that does not contain a solvent with heat and applying it to the base material layer or hard coat layer. After applying an adhesive containing or not containing a solvent on the peelable sheet by the above method and providing an adhesive sheet, the adhesive sheet is placed between the objects to be adhered. It can be provided by a method of sandwiching. After providing the adhesive layer, an aging treatment may be further performed. In addition, the thickness of the adhesive layer is not particularly limited, and the thickness can be arbitrarily set so as to ensure the adhesive strength. is preferred.

As a method for applying the adhesive, a known method can be used, and specific examples include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like.

The decorative film may further have a colored layer. The colored layer is laminated to give the decorative film a design property. , can be freely provided as long as it does not become the outermost layer. In addition to a single color, the coloring may include various decorations such as pictures/patterns, metallic tones, characters, and patterns, and multiple layers of different colored layers may be laminated.

A method for obtaining a colored layer will be described. The colored layer is obtained by applying a colored curable composition to the base layer and drying it, applying it to the base layer, drying it, and aging it, and applying it to the base layer and irradiating it with light. method, a method of printing on a base material layer and drying it, a method of printing on a base material layer and irradiating it with light, a method of obtaining it by vapor-depositing a metal on a base material layer, and the like. The thickness of the colored layer is not particularly limited as long as the intended color, pattern, etc. can be recognized, but from the viewpoint of moldability, it is preferably 500 μm or less.

As a method for providing the colored layer on the base material layer, known methods can be used, and specific examples include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating, silk screen printing, and offset. Printing, gravure printing, inkjet printing, vapor deposition, etc. can be mentioned.

The decorative film can be produced into a decorative molding by various molding methods such as vacuum molding, air pressure molding, TOM molding, injection molding, in-mold molding, press molding, and stamping molding.
Targets for providing a colored layer from the viewpoints of blocking prevention during decorative film manufacturing, scratch prevention, scratch prevention during molding, mold trace prevention, and contamination prevention after molding until the decorative molded body is used. A peelable protective film can be further provided on (eg, the substrate layer).
In addition, when the decorative film is attached to the object to be decorated using an adhesive layer, it can be peeled off from the adhesive layer provided inside the decorative film from the viewpoint of blocking prevention. A protective film may also be provided.

The protective film is not particularly limited, and a known plastic film or paper film can be appropriately selected and used. Examples of films that can be used as protective films include polyethylene films, polypropylene films, polyester films, polycarbonate films, polymethyl methacrylate films, polyamide films, polyimide films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, and polystyrene films. Films, polyacrylonitrile films, aluminum foils, papers, and the like can be used, but there is no limitation, and a laminate of one or more types can be used. In addition, the protective film may be subjected to peeling treatment or adhesive treatment on the plastic film.

As a method of providing a protective film on a decorative film, a method of applying a coating liquid to a base material layer, drying it, and laminating a protective film when a hard coat layer or an adhesive layer is provided; Examples include a method in which a coating liquid is applied, dried, and if necessary aged to provide a hard coat layer and an adhesive layer, and then the substrate layer and the decorative film are laminated. In addition, when the hard coat layer is provided on the protective film first, it may be bonded using an adhesive as necessary.

Decorative films have various aspects (layer structure). Specific examples of this aspect are shown below.
An embodiment having only a hard coat layer and a substrate layer.
An embodiment having a hard coat layer, a substrate layer (1a), and a substrate layer (1b) is shown. The first substrate layer (1a) and the second substrate layer (1b) can be provided, for example, by coextrusion.
An embodiment in which an adhesive layer is positioned between the hard coat layer and the base material layer.
An embodiment having a hard coat layer and a substrate layer, and having a colored layer on the opposite side of the substrate layer (the side opposite to the hard coat layer).
An embodiment having a hard coat layer, a substrate layer and a colored layer, wherein the colored layer is positioned between the hard coat layer and the substrate layer.
It has a hard coat layer, a substrate layer, an adhesive layer and a colored layer, the adhesive layer is located between the hard coat layer and the substrate layer, and the side opposite to the substrate layer (the adhesive layer is provided) An embodiment having a colored layer on the side opposite to the side where the layer is on.
Having a hard coat layer, a first substrate layer (1a), a second substrate layer (1b), a first adhesive layer (2a), and a second adhesive layer (2b), The adhesive layer (2a) is between the hard coat layer and the first substrate layer (1a), and the second adhesive layer (2b) is between the first substrate layer (1a) and the second substrate. An embodiment located in the material layer (1b).
It has a hard coat layer, a base layer, a colored layer, and an adhesive layer, the colored layer is located on the opposite side of the base layer (the side opposite to the hard coat layer), and the hard coat layer and an adhesive layer are respectively located on the surface.
An embodiment having a hard coat layer and a substrate layer, and having an adhesive layer on the side of the substrate layer that is not opposed to the hard coat layer (the side opposite to the side where the hard coat layer is provided).

<Decorative molding>
A decorative molded article (decorative molded article) is a molded article including a decorative film (a molded article to be decorated, for example, a molded article whose surface is covered with a decorative film), and parts other than the decorative film. [For example, the molded body to be coated (hereinafter referred to as the body to be decorated)] is not particularly limited in material, and known materials can be used.

Examples of materials that can be used as the object to be decorated include wood, paper, metal, plastic, fiber-reinforced plastic, rubber, glass, minerals, clay, etc., and may be used alone or in combination of two or more. can be done.

Examples of plastics include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, epoxy resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, poly(meth)acrylate, polycarbonate, polyamide, polyimide. , polyphenylene ether, polyphenylene sulfide, polyester, polytetrafluoroethylene, etc., and can be used singly or in combination of two or more.

Examples of fiber-reinforced plastics include carbon-fiber-reinforced plastics, glass-fiber-reinforced plastics, aramid-fiber-reinforced plastics, and polyethylene fiber-reinforced plastics.

Examples of metals include hot rolled steel, cold rolled steel, galvanized steel, electrogalvanized steel, hot dip galvanized steel, alloyed hot dip galvanized steel, zinc alloy plated steel, copper plated steel, zinc-nickel plated steel, Zinc-aluminized steel, iron-galvanized steel, aluminized steel, aluminum-galvanized steel, tin-plated steel, aluminum, stainless steel, copper, aluminum alloy, electromagnetic steel, etc., one or more Can be used in combination. In addition, an anti-agent layer or the like may be provided on the surface of the metal.

There is no particular limitation on the method for integrating the decorative film and the object to be decorated, and they can be integrated by a known integration method. As an integration method, for example, insert molding, in-mold molding, vacuum molding, air pressure molding, TOM molding, press molding, or the like can be used.

For example, after preforming the decorative film into a desired shape, the object to be decorated or its material (for example, plastic or fiber reinforced plastic) is injection molded so that the hard coat layer side becomes the outermost layer, and the decorative molding is performed. You can get a body.
Alternatively, a molded body (object to be decorated) is obtained from plastic, fiber-reinforced plastic, metal, or the like, and a decorative film is placed on the surface of the molded body, or a preformed body in which the decorative film is preformed into a desired shape. can also be obtained by adhering such that the hard coat layer side is the outermost layer.

In the decorative molding, the hard coat layer side of the decorative film is usually positioned as the outermost layer. As described above, the hard coat layer of the decorative film may be provided with a protective film to protect appearance defects that may occur in each process such as coating, drying, aging, and molding integration. In the case where the molded decorative molded article is used, it is preferable that the protective film is peeled off.

The present invention is not limited to the above-described embodiments, and various modifications are possible, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the present invention. .

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

In the following, unless otherwise specified, "%" means "mass (weight)%" and "parts" means "mass (weight) parts".

Various physical properties were measured and evaluated by the following methods.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)]
The weight average molecular weight and molecular weight distribution of the resin were determined by polystyrene conversion using gel permeation chromatography (GPC). The apparatus and measurement conditions used for the measurement are as follows.
System: Tosoh GPC system HLC-8320
Measurement side column configuration Guard column: TSKguardcolumn SuperHZ-L manufactured by Tosoh
・ Separation column: TSKgel SuperHZM-M, manufactured by Tosoh, 2 columns connected in series Reference side column configuration ・ Reference column: TSKgel SuperH-RC, manufactured by Tosoh
Developing solvent: Chloroform (manufactured by Wako Pure Chemical Industries, special grade)
Flow rate of developing solvent: 0.6 mL / min Standard sample: TSK standard polystyrene (manufactured by Tosoh, PS-oligomer kit)
Column temperature: 40°C

[Glass transition temperature (Tg)]
The glass transition temperature was measured according to JIS K7121-1987. Specifically, using a differential scanning calorimeter ("Thermo plus EVO DSC-8230" manufactured by Rigaku), a sample of about 10 mg was heated from room temperature to 200 ° C. in a nitrogen gas atmosphere (heating rate 20 ° C./min. ) from the DSC curve obtained by the starting point method. α-alumina was used as a reference.

[Melt flow rate (MFR)]
The melt flow rate was measured at a temperature of 230° C. and a load of 3.8 kg (37 N) in accordance with JIS K 7210-1:2014 A method.

[Shear viscosity]
The shear viscosity was measured using a twin-bore barrel type capillary rheometer RH10 manufactured by Rosand. Using a long die with a diameter of 1 mm and a length of 16 mm and a short die with a diameter of 1 mm and a length of 0.25 mm, the measurement was performed at a measurement temperature of 240° C. and a shear rate of 1000/s. The shear viscosity was calculated by performing Bergley correction on the value thus obtained.

[Refractive index]
The refractive index was measured using a refractometer (manufactured by Atago Co., Ltd., multi-wavelength Abbe refractometer, DR-M2) in accordance with the JIS K7142:2008 A method, and the molded article 1 having a thickness of 3 mm.
After drying the obtained pellets at 100 ° C. for 12 hours or more, molded body 1 was molded using an injection molding machine (NS40-5A manufactured by Nissei Plastics Co., Ltd.) at a molding temperature of 230 ° C., a mold temperature of 100 ° C., and a mold size. It was produced with a size of 100 mm×100 mm×thickness of 3 mm.
Using Atago RE-1196 (bromonaphthalene solution (nD: 1.65)) as an intermediate liquid, the refractive index (nD) at a wavelength of 589 nm at 23° C. was measured.

[Total light transmittance (Tt)]
The total light transmittance is measured using a turbidity meter (NDH 5000, manufactured by Nippon Denshoku Industries Co., Ltd.), in accordance with JIS K7361-1: 1997, using a molded article 1 having a thickness of 3 mm or a molded article having a predetermined thickness. (Film) 2 was measured.
The thickness of the film was measured using a Digimatic micrometer (manufactured by Mitutoyo Corporation). A film sample to be measured was obtained from the central portion of the film in the width direction (hereinafter, the same applies to the measurement of the film).
In addition, molded article 1 is for Examples 1 to 12 and reference examples 1 to 4 (and acrylic resin and polycarbonate resin used in these), molded article 2 is for other examples and reference examples ( Films having a thickness of 75 μm or 50 μm produced in Examples 13 to 16 and Reference Examples 5 to 7 (hereinafter the same).

[Haze]
Haze is measured using a turbidity meter ("NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the provisions of JIS K7136. was measured.

[Yellowness index (YI)]
Yellowness is measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3600), a C2 degree light source, a wavelength range of 380 nm to 780 nm, in accordance with the provisions of JIS K7373: 2006. It was measured.

[b ^* value]
The b ^* value was measured using a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd.: Colormeter ZE6000) in accordance with JIS Z 8729 and measuring a molded product (film) 2 having a predetermined thickness.

[Pencil hardness]
Pencil hardness is measured according to JIS K5600-5-4: 1999, using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) with a load of 750 g and a molded body 1 having a thickness of 3 mm or a molded body having a predetermined thickness ( Film) 2 was measured.

[Martens hardness]
Martens hardness was evaluated by a method based on ISO-14577-1 using an ultra-micro hardness tester (Fischer Scope HM-2000, manufactured by Fisher Instruments Co., Ltd.) on a compact 1 having a thickness of 3 mm.
The measurement conditions used a square pyramid Vickers indenter (facing angle a = 136°); maximum test load 3 mN; application time 60 seconds when applying load; creep time 5 seconds; application time 20 seconds when reducing load; Temperature: room temperature; and obtained by averaging the values measured three times.

[Tensile strength test]
It was measured according to JIS K 7127:1999 using an autograph (AGS-X manufactured by Shimadzu Corporation). Specifically, two types of test films with a length of 150 mm and a width of 10 mm whose longitudinal directions are the MD direction and the TD direction are allowed to stand at 23 ° C. and 50% RH for 1 hour or more, and then the test speed is 5 mm / min. , the test was carried out under the condition that the distance between the gauge lines was 25 mm, and the elastic modulus, tensile strength and elongation at break were measured. The average value of five samples in each direction was used as the measurement result.

[MIT (number of folding endurance)]
MIT was measured according to JIS P8115. Specifically, two types of test films with a length of 90 mm and a width of 15 mm whose longitudinal directions are the MD direction and the TD direction were left to stand at 23 ° C. and 50% RH for 1 hour or more before use. Using a fatigue tester (Toyo Seiki, DA type), the test was performed under the conditions of a bending angle of 135 °, a bending speed of 175 cpm, and a load of 200 g. asked.

[Tear strength (trouser tear strength)]
The tear strength was measured according to JIS K 7128-1:1998. Specifically, the film is cut into a size of 120 mm × 30 mm so that the longitudinal direction is the MD direction and the TD direction, and the test piece is allowed to stand in an atmosphere of 23 ° C. and 50% relative humidity for 1 hour or more. Then, the test was performed at a test speed of 200 mm / min using an autograph (AGS-X, manufactured by Shimadzu Corporation), and the average tear force of 35 mm excluding 20 mm at the start of tearing and 5 mm before the end of tearing was calculated. The average value of five samples in each direction was used as the measurement result.

[Film impact strength]
The film impact strength was measured in accordance with ASTM D3420 in an atmosphere of 23° C. and 50% relative humidity using a film impact tester (manufactured by Tester Sangyo Co., Ltd., product number: BU-302).

[Heat shrinkage]
By cutting the produced film, three square-shaped samples having a length of 100 mm and a width of 100 mm were produced. The lengths of the four sides of the sample (La1 and La2 in the MD direction, La3 and La4 in the TD direction) were measured with a digital vernier caliper. Next, the sample was stored in a constant temperature bath at 100° C. After 1 hour, the sample was taken out from the constant temperature bath and the lengths (Lb1, Lb2, Lb3, Lb4) of the four pieces of the sample were measured again.
Next, the heat shrinkage rate on each side of the three samples is expressed by the formula:
[Heat shrinkage rate (%)] = (La - Lb) / La x 100
(In the formula, La is the length of one side before the test, and Lb is the length of one piece after the test)
, and the average value of the heat shrinkage rate of each side of the three samples obtained was obtained. Next, after obtaining the sum of the average values of La1 and La2, the sum is divided by 2 to obtain the heat shrinkage rate in the MD direction. Similarly, the heat shrinkage rate in the TD direction is obtained from the average value of La3 and La4. asked.

[Phase difference]
The in-plane retardation Re and the thickness direction retardation Rth were determined using a retardation film/optical material inspection device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.). The thickness direction retardation Rth is the average refractive index of the molded body measured by an Abbe refractometer, and the in-plane retardation Re (40°) measured by the above apparatus with the film tilted 40° with respect to the tilt axis. Using the refractive indices nx, ny and nz obtained from , and the thickness d (nm) of the molded body, it was calculated by the formula Rth={(nx+ny)/2−nz}×d. nx is the refractive index in the slow axis direction in the plane of the molded body, ny is the refractive index in the direction perpendicular to the slow axis direction (fast axis direction) in the plane of the molded body, and nz is the refractive index of the molded body is the refractive index in the thickness direction. Note that Re (40°) is obtained from Re (S40°) obtained with the slow axis as the tilt axis and Re (F40°) with the direction perpendicular to the slow axis in the plane of the compact as the tilt axis. The larger value was chosen.

[Photoelastic coefficient (Cd)]
The photoelastic coefficient (Cd) was evaluated as follows. First, the resin composition to be evaluated was heat-press molded to obtain a film (unstretched film) having a thickness of 100 μm. Next, the obtained film was cut into a rectangle with a width of 7 mm to obtain a test piece. Next, the test piece was mounted on the tensile tester stage installed in the retardation film/optical material inspection device (manufactured by Otsuka Electronics Co., Ltd., RETS-100) with a chuck distance of 30 mm, and the elongation stress (σR) was tested. The birefringence Δn for light with a wavelength of 590 nm was measured while applying to the strip. The measurement temperature was 23° C., and the tensile speed (chuck moving speed) was 5 mm/min. From the relationship between the measured birefringence Δn and the tensile stress (σR) applied to the test piece, the slope Δn/σR was obtained by the method of least squares, and this was taken as the photoelastic coefficient (Cd) of the resin composition. For the calculation of Cd, data in which the tensile stress σR was in the range of 2.5 MPa≦σR≦10 MPa was used. Δn is Δn=|nx−ny|.

[Proportion of lactone ring structure contained in acrylic resin]
First, based on the amount of weight loss that occurs when all hydroxyl groups are dealcoholized as methanol from the polymer composition obtained by polymerization, from 150 ° C. before the start of weight loss in dynamic TG measurement to before the decomposition of the polymer starts. The dealcoholization reaction rate was obtained from the weight loss due to the dealcoholization reaction up to 300°C.
That is, the weight loss rate is measured between 150° C. and 300° C. in the dynamic TG measurement of a polymer having a lactone ring structure, and the measured weight loss rate obtained is defined as (X). On the other hand, from the composition of the polymer, the theoretical weight loss rate (i.e., 100 (Y) is the weight loss rate calculated on the assumption that a % dealcoholization reaction has occurred.
The theoretical weight loss rate (Y) is, more specifically, the molar ratio of the raw material monomer having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material unit in the polymer composition. It can be calculated from the content of the polymer.
These values (X) and (Y) are calculated according to the dealcoholization formula:
1-(actual weight reduction rate (X)/theoretical weight reduction rate (Y))
, the value is expressed in % to obtain the dealcoholization reaction rate.
The proportion of the lactone ring structure in the pellets obtained in Production Example 1, which will be described later, is calculated. The theoretical weight loss rate (Y) of this polymer was found to be 32 for methanol, 116 for methyl 2-(hydroxymethyl)acrylate, and 116 for methyl 2-(hydroxymethyl)acrylate. The content (mass ratio) of in the polymer is 13% by mass, so (32/116)×13≈3.59% by mass. On the other hand, the weight reduction rate (X) measured by dynamic TG measurement was 0.08% by mass. When these values are applied to the above dealcoholization formula, 1−(0.08/3.59)≈0.978, so the dealcoholization conversion is 97.8%.
In the case of Production Example 1, the content of 2-(hydroxymethyl)methyl acrylate in the copolymer is 13.0% by mass, the calculated dealcoholization reaction rate is 97.8% by mass, and the molecular weight of 2-( Since the formula weight of the lactone cyclic structural unit formed when methyl hydroxymethyl)acrylate is condensed with methyl methacrylate is 170, the content of lactone rings in the copolymer is 8.6 (13. 0×0.978×170/116)% by mass.

[Acid value]
Acid value was measured by the following method. First, 0.15 g of polymer was dissolved in 24.94 g of methylene chloride. 14.85 g of methanol was added to the resulting solution and stirred for 3 hours. Two drops of a 1% by weight phenolphthalein ethanol solution were then added to this solution. A 0.1N sodium hydroxide aqueous solution was added to the resulting solution while stirring, and stirring was continued at room temperature for 1 hour. At this time, the amount of the 0.1N aqueous sodium hydroxide solution added is defined as Aml. Next, 0.1N hydrochloric acid was added dropwise to this solution. The amount of 0.1N hydrochloric acid added until the color of the solution (reddish purple) disappeared is defined as Bml.
Next, a mixture of 24.94 g of methylene chloride and 14.85 g of methanol was prepared. Two drops of a 1% by weight phenolphthalein ethanol solution were added to this mixture. Next, a 0.1N sodium hydroxide aqueous solution was added to the mixture while stirring, and stirring was continued at room temperature for 1 hour. At this time, the amount of 0.1N aqueous sodium hydroxide solution added is defined as Cml. Next, 0.1N hydrochloric acid was added dropwise to this mixture. Dml is defined as the amount of 0.1N hydrochloric acid added until the color of the mixture disappears (reddish purple).
The acid value (mmol/g) of the polymer was obtained from the following formula. The acid value represents the amount of sodium hydroxide required to neutralize the acidic groups contained in 1 g of the polymer and the acidic groups generated by hydrolysis of the acid anhydride groups. there is
[Acid value (mmol / g)] = 0.1 × [(A - B) - (C - D)] / 0.15

(Production Example 1 [Production of acrylic resin (B1)])
6.5 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA) and 43.5 parts by mass of methyl methacrylate (MMA) were placed in a reaction vessel equipped with a stirrer, temperature sensor, cooling tube, nitrogen inlet tube and dropping pump. 90.7 parts by mass of toluene and 0.05 parts by mass of tris(2,4-di-tert-butylphenyl) phosphite were charged, and the temperature was raised to 105° C. while passing nitrogen.
As an initial initiator, a solution consisting of 4.3 parts by mass of toluene and 0.22 parts by mass of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570) was added dropwise over 8 minutes. C. to 110.degree. C. solution polymerization was carried out. After 22 minutes, a solution consisting of 5.0 parts by mass of toluene as a dropping initiator and 0.28 parts by mass of t-amylperoxyisononanoate (Luperox (registered trademark) 570, manufactured by Arkema Yoshitomi Co., Ltd.) was added for 180 minutes. dripped over. Twenty-five minutes after the initial initiator was added, a solution consisting of 6.5 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA) and 43.5 parts by mass of methyl methacrylate (MMA) was added dropwise over 180 minutes. While solution polymerization was carried out at 105° C. to 110° C., aging was further carried out for 1.5 hours.
To the resulting polymerization solution, a solution consisting of 1.25 parts by mass of toluene and 0.075 parts by mass of stearyl phosphate (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) is added as a catalyst for the cyclization condensation reaction (cyclization catalyst). was added, and the cyclization condensation reaction to form the lactone ring structure was allowed to proceed under reflux at about 90°C to 110°C for 1.5 hours.
Next, the resulting polymerization solution is passed through a shell and tube heat exchanger maintained at 220° C. to complete the cyclization condensation reaction, and a leaf disk type polymer filter (filtration accuracy of 5 μm) is placed at the tip. The polymerization solution was devolatilized by introducing it into a vent-type screw twin-screw extruder (L/D=52) at a processing rate of 90 parts by mass/hour in terms of resin amount. The number of rear vents of the vent-type screw twin-screw extruder used was 1, and the number of fore vents was 4 (referred to as the first, second, third, and fourth vents from the upstream side), the barrel temperature was 220 ° C., and the pressure was reduced. The pressure was 13.3 to 400 hPa (10 to 300 mmHg). During devolatilization, ion-exchanged water was introduced from behind the first, second, and third vents at a rate of 1.3 parts by mass/hour.

The resulting resin pellet (B1) has a weight average molecular weight of 88,000, a molecular weight distribution of 2.2, a glass transition temperature of 123° C., a melt flow rate of 4.5, a shear viscosity of 221 Pa s, and a refractive index of 1.4974, the ratio of the ring structure was 18.6% by mass, and the acid value was 0.2 mmol/g or less.

(Production Example 2 [Production of acrylic resin (B2)])
10 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA), 40 parts by mass of methyl methacrylate (MMA), tris phosphite ( 0.025 parts by mass of 2,4-di-tert-butylphenyl) and 50 parts by mass of toluene as a polymerization solvent were charged. Next, while introducing nitrogen gas into the reaction vessel, the temperature was raised to 105°C, and when the reflux accompanying the temperature rise began, tertiary amyl peroxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered)) was used as a polymerization initiator. Trademark) 570) 0.05 parts by mass was added. At the same time, 0.10 parts by mass of the tertiary amyl peroxy isononanoate was started to be added dropwise, and solution polymerization was allowed to proceed under reflux at about 105 to 110° C. while dropping this over 2 hours. After completion of dropping, the reaction vessel was kept heated for 4 hours for aging.

Next, 0.05 parts by mass of stearyl phosphate (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) is added to the polymerization solution thus obtained as a catalyst for the cyclization reaction, and the temperature is maintained at about 90°C to 110°C. The cyclization condensation reaction forming the lactone ring structure was allowed to proceed under reflux for 2 hours.

Next, the obtained polymerization solution is passed through a shell and tube heat exchanger maintained at 240° C. to complete the cyclization condensation reaction, and a leaf disk type polymer filter (filtration accuracy of 5 μm) is placed at the tip. The polymerization solution was devolatilized by introducing it into a vent-type screw twin-screw extruder (L/D=52) at a processing rate of 90 parts by mass/hour in terms of resin amount. The number of rear vents of the vent-type screw twin-screw extruder used was 1, and the number of fore vents was 4 (referred to as the first, second, third, and fourth vents from the upstream side), and the third and fourth vents A side feeder was placed between and the barrel temperature was 240° C. and the degree of vacuum was 13.3 to 400 hPa (10 to 300 mmHg). During devolatilization, 0.6 parts by mass/hour of a separately prepared solution of a cyclization catalyst deactivator was added from behind the second vent at a rate of 1.3 parts by mass/hour of ion-exchanged water. It was charged from behind the 3rd vent at the charging speed. As a solution of the cyclization catalyst deactivator, a solution obtained by dissolving 1.0 parts by mass of zinc octylate (manufactured by Nihon Kagaku Sangyo, trade name: Nikka Octix Zinc 10% by mass) in 0.3 parts by mass of toluene was used. there was.

The resulting resin pellet (B2) has a weight average molecular weight of 116,000, a molecular weight distribution of 2.6, a glass transition temperature of 130 ° C., a melt flow rate of 0.8, a shear viscosity of 321 Pa s, and a refractive index of 1.4999, the ratio of the ring structure was 28.6% by mass, and the acid value was 0.3 mmol/g or less.

(Production Example 3 [Production of acrylic resin (B3)])
11.5 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA) and 38.5 parts by mass of methyl methacrylate (MMA) were placed in a reaction vessel equipped with a stirrer, temperature sensor, cooling tube, nitrogen inlet tube and dropping pump. 90.7 parts by mass of toluene, 0.05 parts by mass of tris(2,4-di-tert-butylphenyl) phosphite, and heated to 105° C. while passing nitrogen.
As an initial initiator, a solution consisting of 4.3 parts by mass of toluene and 0.22 parts by mass of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570) was added dropwise over 8 minutes. C. to 110.degree. C. solution polymerization was carried out. After 22 minutes, a solution consisting of 5.0 parts by mass of toluene and 0.22 parts by mass of t-amylperoxyisononanoate (Luperox (registered trademark) 570, manufactured by Arkema Yoshitomi Co., Ltd.) as a dropping initiator was added for 170 minutes. dripped over. Further, 25 minutes after the initial initiator was added, a solution consisting of 11.5 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA) and 38.5 parts by mass of methyl methacrylate (MMA) was added dropwise over 180 minutes. While solution polymerization was carried out at 105° C. to 110° C., aging was further carried out for 1.5 hours.
To the obtained polymerization solution, a solution consisting of 1.25 parts by mass of toluene and 0.30 parts by mass of stearyl phosphate (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) is added as a catalyst for the cyclization condensation reaction (cyclization catalyst). was added, and the cyclization condensation reaction to form the lactone ring structure was allowed to proceed under reflux at about 90°C to 110°C for 2 hours.
Next, the obtained polymerization solution is passed through a shell and tube heat exchanger maintained at 240° C. to complete the cyclization condensation reaction, and a leaf disk type polymer filter (filtration accuracy of 5 μm) is placed at the tip. The polymerization solution was devolatilized by introducing it into a vent-type screw twin-screw extruder (L/D=52) at a processing rate of 90 parts by mass/hour in terms of resin amount. The number of rear vents of the vent-type screw twin-screw extruder used was 1, and the number of fore vents was 4 (referred to as the first, second, third, and fourth vents from the upstream side), the barrel temperature was 240 ° C., and the pressure was reduced. The pressure was 13.3 to 400 hPa (10 to 300 mmHg). At the time of devolatilization, 0.30 parts of a mixed solution of a bluing agent and an antioxidant prepared separately was added from behind the first and third vents at a rate of 1.3 parts by mass/hour of ion-exchanged water. The charge rate was in parts by mass/hour and was introduced from behind the second vent. As a mixed solution of a bluing agent and an antioxidant, 0.27 parts by mass of a solution obtained by dissolving 1.0 parts by mass of a bluing agent (Sumiplast (registered trademark) VioletB manufactured by Sumika Chemtex Co., Ltd.) in 99 parts by mass of toluene, A solution containing 3.6 parts by mass of two kinds of antioxidants (Irganox 1010 manufactured by BASF Japan and Adekastab AO-412S manufactured by ADEKA) and 112.5 parts by mass of toluene was used.

The resulting resin pellet (B3) has a weight average molecular weight of 85,000, a molecular weight distribution of 2.0, a glass transition temperature of 132° C., a melt flow rate of 3.1, a shear viscosity of 290 Pa s, and a refractive index of 1.5004, the ratio of the ring structure was 28.8% by mass, and the acid value was 0.3 mmol/g or less.

(Production Example 4 [Production of acrylic resin (B4)])
12 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA), 83.5 parts by mass of methyl methacrylate, and 90.5 parts by mass of toluene were added to a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, a nitrogen inlet tube and a dropping pump. 4 parts by mass, 0.05 parts by mass of tris(2,4-di-tert-butylphenyl) phosphite, and 0.07 parts by mass of n-dodecylmercaptan as a chain transfer agent were charged, and the temperature was raised to 105°C while passing nitrogen. did.
As an initial initiator, 0.09 parts by mass of t-amyl peroxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570) was added, and after 5 minutes, 4.5 parts by mass of styrene and 8.14 parts by mass of toluene were added. Part, dropping initiator t-amyl peroxy isononanoate (manufactured by Arkema Yoshitomi Co., Ltd., Luperox (registered trademark) 570) 0.179 parts by mass solution is dropped over 2 hours while solution polymerization at 100 ° C. to 110 ° C. and aged for 4 hours.
To the resulting polymerization solution, 0.075 parts by mass of stearyl phosphate (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added as a catalyst for the cyclization condensation reaction (cyclization catalyst), and the mixture was heated to about 90°C to 110°C. The cyclization condensation reaction to form the lactone ring structure was allowed to proceed under reflux for 1.5 hours.
Next, the obtained polymerization solution is passed through a shell and tube heat exchanger maintained at 240° C. to complete the cyclization condensation reaction, and a leaf disk type polymer filter (filtration accuracy of 5 μm) is placed at the tip. The polymerization solution was devolatilized by introducing it into a vent-type screw twin-screw extruder (L/D=52) at a processing rate of 90 parts by mass/hour in terms of resin amount. The number of rear vents of the vent-type screw twin-screw extruder used was 1, and the number of fore vents was 4 (referred to as the first, second, third, and fourth vents from the upstream side), the barrel temperature was 240 ° C., and the pressure was reduced. The pressure was 13.3 to 400 hPa (10 to 300 mmHg). During devolatilization, 0.3 parts by mass of a separately prepared solution of a cyclization catalyst deactivator was added from behind the first and second vents at an injection rate of 1.3 parts by mass/hour of ion-exchanged water. Charged from behind the 3rd vent at a charge rate of /hour. As a solution of the cyclization catalyst deactivator, a solution obtained by dissolving 1.0 parts by mass of zinc octylate (manufactured by Nihon Kagaku Sangyo, trade name: Nikka Octix Zinc 10% by mass) in 0.3 parts by mass of toluene was used. there was.

The resulting resin pellet (B4) has a weight average molecular weight of 130,000, a molecular weight distribution of 2.7, a glass transition temperature of 123 ° C., a melt flow rate of 1.6, a shear viscosity of 262 Pa s, and a refractive index of 1.5013, the ratio of the ring structure was 16.9% by mass, and the acid value was 0.2 mmol/g or less.

(Production Example 5 [Production of acrylic resin (acrylic resin composition) (B5)])
Pellets of the acrylic resin (B1) obtained in Production Example 1 and AS resin (styrene-acrylonitrile copolymer, styrene/acrylonitrile ratio: 73% by mass/27% by mass, weight average molecular weight: 220,000) were mixed into B1/AS resin. = 100/4 by kneading at 240°C using a twin-screw extruder (φ = 30 mm, L/D = 40) to obtain resin pellets (B5).
The resulting resin pellet (B5) has a weight average molecular weight of 90,000, a molecular weight distribution of 2.3, a glass transition temperature of 122 ° C., a melt flow rate of 4.2, a shear viscosity of 221 Pa s, and a refractive index of was 1.5002.

(Production Example 6 [Production of acrylic resin (B6)])
70 parts by mass of methyl methacrylate (MMA), 30 parts by mass of methyl 2-(hydroxymethyl)acrylate (RHMA), methyl isobutyl ketone ( MIBK) and methyl ethyl ketone (MEK) (mass ratio 9:1) of 67 parts by mass was charged.
Next, while flowing nitrogen into the reaction vessel, the contents of the reaction vessel were heated to 105° C. After the start of reflux, t-amyl peroxyisononanoate (trade name: Lupazol 570, Atofina Yoshitomi (trade name: Lupazol 570, Atofina Yoshitomi) was used as an initiator. At the same time, an initiator solution consisting of 0.12 parts by mass of t-amyl peroxyisononanoate and 33 parts by mass of a mixed solvent of MIBK and MEK (mass ratio 9:1). was added dropwise over 3 hours, solution polymerization was carried out under reflux (about 95 to 110°C). After dropping the initiator solution, aging was further performed for 4 hours.
To the resulting polymer solution, 0.2 part by mass of an octyl phosphate/dioctyl phosphate mixture (trade name: Phoslex A-8, manufactured by Sakai Chemical Industry Co., Ltd.) was added, and the mixture was refluxed at about 85°C to 100°C for 2 hours. A cyclization condensation reaction was allowed to proceed to form the lactone ring structure.
Next, the obtained polymerization solution is passed through a shell and tube heat exchanger maintained at 240° C. to complete the cyclization condensation reaction, and a leaf disk type polymer filter (filtration accuracy of 5 μm) is placed at the tip. The polymerization solution was devolatilized by introducing it into a vent-type screw twin-screw extruder (L/D=52) at a processing rate of 90 parts by mass/hour in terms of resin amount. The number of rear vents of the vent-type screw twin-screw extruder used was 1, and the number of fore vents was 4 (referred to as the first, second, third, and fourth vents from the upstream side), the barrel temperature was 240 ° C., and the pressure was reduced. The pressure was 13.3 to 400 hPa (10 to 300 mmHg). During devolatilization, 0.3 parts by mass of a separately prepared solution of a cyclization catalyst deactivator was added from behind the first and second vents at an injection rate of 1.3 parts by mass/hour of ion-exchanged water. Charged from behind the 3rd vent at a charge rate of /hour. As a solution of the cyclization catalyst deactivator, a solution obtained by dissolving 1.0 parts by mass of zinc octylate (manufactured by Nihon Kagaku Sangyo, trade name: Nikka Octix Zinc 10% by mass) in 0.3 parts by mass of toluene was used. there was.

The resulting pellet (B6) had a weight average molecular weight of 127,000, a molecular weight distribution of 2.8, a glass transition temperature of 140°C, a melt flow rate of 0.5, a shear viscosity of 366 Pa s, and a refractive index of 1. .5041, the ratio of the ring structure was 41.9% by mass, and the acid value was 0.4 mmol/g or less.

Table 1 shows a summary of the acrylic resin (or resin composition) (B) obtained in each production example.
In Table 1 below, the values in parentheses for the refractive index and shear viscosity in Production Example 5 are for the composition (acrylic resin composition) with the AS resin.

For the polycarbonate resin (A), a commercially available polycarbonate resin having an alicyclic skeleton (manufactured by Mitsubishi Chemical Corporation, Durabio, isosorbide and other alicyclic diols (molar ratio of about 50/50 to 70/30) was mixed with dihydroxy compound), and a polycarbonate resin having an aromatic skeleton (Mitsubishi Engineering-Plastics, Iupilon HL4000, a polycarbonate resin containing 2,2-bis(4-hydroxyphenyl)propane as a dihydroxy compound)].

The details and physical property values are shown in Table 2 below.

(Example 1)
Pellets of polycarbonate resin (A1) having an alicyclic skeleton and acrylic resin (B1) obtained in Production Example 1 were extruded in a twin-screw extruder (φ = 30 mm, L/D=40) and kneaded at 240° C. to obtain resin pellets.
Using the obtained pellets, a molded body (for example, after drying at 100 ° C. for 12 hours or more, using an injection molding machine (NS40-5A manufactured by Nissei Plastics Co., Ltd.), molding temperature 230 ° C., mold temperature 100 ° C. , 100 mm×100 mm×thickness 3 mm, etc.).

(Example 2)
A resin pellet and a molded body were produced in the same manner as in Example 1, except that the acrylic resin (B2) pellets obtained in Production Example 2 were used.

(Example 3)
A resin pellet and a molded body were produced in the same manner as in Example 1, except that the acrylic resin (B3) pellets obtained in Production Example 3 were used.

(Example 4)
Pellets of the polycarbonate resin (A2) having an alicyclic skeleton and the acrylic resin (B3) obtained in Production Example 3 were extruded in a twin-screw extruder (φ = 30 mm, L/D=40) and kneaded at 240° C. to obtain resin pellets.
Using the obtained pellets, a molded body (for example, after drying at 100 ° C. for 12 hours or more, using an injection molding machine (NS40-5A manufactured by Nissei Plastics Co., Ltd.), molding temperature 230 ° C., mold temperature 100 ° C. , 100 mm×100 mm×thickness 3 mm, etc.).

(Example 5)
A resin pellet and a molded body were produced in the same manner as in Example 4, except that the mass ratio of A2/B3 was set to 70/30.

(Example 6)
A resin pellet and a molded body were produced in the same manner as in Example 4, except that the mass ratio of A2/B3 was changed to 50/50.

(Example 7)
A resin pellet and a molded body were produced in the same manner as in Example 3, except that pellets of the polycarbonate resin (A3) having an alicyclic skeleton were used.

(Example 8)
A resin pellet and a molded body were produced in the same manner as in Example 1, except that the acrylic resin (B4) pellets obtained in Production Example 4 were used.

(Example 9)
A resin pellet and a molded body were produced in the same manner as in Example 1, except that the acrylic resin (B5) pellets obtained in Production Example 5 were used.

(Example 10)
A resin pellet and a molded body were produced in the same manner as in Example 1, except that the acrylic resin (B6) pellets obtained in Production Example 6 were used.

(Reference example 1)
In Example 1, a commercially available acrylic resin (manufactured by Sumitomo Chemical Co., Ltd., Sumipex MH, weight average molecular weight: 93,000, molecular weight distribution: 2.0, glass transition temperature: 110°C, melt flow rate: 2.0, refractive index: 1.0) was used. 4924) were used in the same manner as in Example 1 to prepare resin pellets and molded articles.

(Reference example 2)
Pellets of the polycarbonate resin (A4) having an aromatic skeleton and the acrylic resin (B3) obtained in Production Example 3 were extruded in a twin-screw extruder (φ = 30 mm, L /D=40) was kneaded at 260.degree.

(Reference example 3)
Using a polycarbonate resin (A2) having an alicyclic skeleton, a molded body (for example, after drying at 100 ° C. for 12 hours or more, using an injection molding machine (NS40-5A manufactured by Nissei Plastics Co., Ltd.), molding temperature 230 ° C., At a mold temperature of 100° C., a molded body of 100 mm×100 mm×thickness 3 mm, etc.) was produced.

(Reference example 4)
Using the acrylic resin (B3) obtained in Production Example 3, a molded body (for example, after drying at 100 ° C. for 12 hours or more, using an injection molding machine (NS40-5A manufactured by Nissei Plastics Co., Ltd.), molding temperature 230 ° C. , at a mold temperature of 100° C., a molded body of 100 mm×100 mm×thickness 3 mm, etc.) was produced.

Table 3 shows the evaluation results of each example and reference example. In Table 3 below, the values in parentheses for the refractive index difference in Example 9 are for the case where _RB is the refractive index of the composition (acrylic resin composition) with the AS resin.

As is clear from the above table, in the examples, it was possible to obtain a resin composition from the polycarbonate resin and the acrylic resin (furthermore with the AS resin) without whitening or the like. And such a resin composition, while being a composition in which different resins are mixed, exhibits high transparency and low colorability, and is excellent in various physical properties (high surface hardness, low photoelastic coefficient, low retardation expression properties, etc.), and a molded body (molten molded body) could be produced.

(Example 11)
Polycarbonate resin (A2) having an alicyclic skeleton and pellets of acrylic resin (B3) obtained in Production Example 3 were mixed in a pellet blender at a weight ratio of A2/B3 = 70/30, and heated at 100°C. After drying for 12 hours or more, an injection molding machine (NS40-5A manufactured by Nissei Plastics Co., Ltd.) was used at a molding temperature of 230 ° C. and a mold temperature of 100 ° C. to produce a molded body of 100 mm × 100 mm × thickness 3 mm. .

(Example 12)
A molded article was produced in the same manner as in Example 11, except that the acrylic resin (B5) pellets obtained in Production Example 5 were used.

Table 4 shows the evaluation results of each example. For comparison, Table 4 also shows the results of Example 5 for comparison with Example 11.

As shown in the above table, in Examples 11 and 12, similarly to the above-described Examples, it is possible to produce a molded article that has high transparency, low coloration, and excellent physical properties without causing whitening or the like. did it.

It was also found that the above molded article can be obtained without using a melt-kneaded acrylic resin and a polycarbonate resin in advance. In particular, due to such a combination of specific resins, even if it is subjected to molding (melt molding) without melt kneading (mixing) such as pelletizing in advance, it is possible to produce an excellent molded body. Moreover, it was unexpected that a molded article with even higher transparency (furthermore, low coloration) was obtained.

(Example 13)
Pellets of the acrylic resin (B4) obtained in Production Example 4 and the polycarbonate resin (A2) having an alicyclic skeleton were extruded into a twin screw extruder (φ = 37 mm) so that the weight ratio of B4/A2 = 80/20. , L/D=34) at 260° C. to obtain resin pellets (C1).
Next, using a vented single-screw extruder, the obtained resin pellets (C1) were subjected to melt film formation at a processing rate of 25 kg/hour. The extruder had a diameter of 65 mm, L/D=32, barrier flight type screw. In addition, a polymer filter (filtration accuracy of 10 μm) and a T-die were provided at the tip of the extruder. The molten resin film after film formation was cast on a cooling roll at 115° C. to obtain an unstretched film with a thickness of 187 μm.
The obtained unstretched film was continuously supplied to an oven longitudinal stretching machine as it was, and stretched in the longitudinal direction at a draw ratio of 2 times at an oven temperature of 135°C. The stretched film was wound up by a winding machine to obtain a longitudinally stretched film roll having an average thickness of 132 μm.
The obtained longitudinally stretched film roll was unwound by a unwinding machine, held by a 2-inch clip at a position of 20 mm from both ends, and supplied to a tenter stretching machine. Then, the film was laterally stretched at an oven temperature of 137° C. at a stretching ratio of 2.6 times. The stretched film was wound up by a winding machine to obtain a roll-shaped film (D1) having an average thickness of 50 μm.

(Example 14)
A roll-shaped film (D2) having an average thickness of 75 μm was obtained in the same manner as in Example 13, except that the longitudinal draw ratio was set to 1.56 times and the transverse draw ratio was set to 2 times in Example 1. Ta.

(Example 15)
In Example 1, the procedure was the same as in Example 13, except that the resin pellets (C2) obtained by kneading so that the weight ratio was B4/A2 = 70/30 were used. Rolls having an average thickness of 50 µm A shaped film (D3) was obtained.

(Example 16)
A roll-shaped film (D4) having an average thickness of 75 μm was obtained in the same manner as in Example 15, except that the longitudinal draw ratio was set to 1.56 times and the transverse draw ratio was set to 2 times. Ta.

(Reference example 5)
A roll-shaped film (D5) having an average thickness of 50 μm was obtained in the same manner as in Example 13, except that the acrylic resin pellets (B4) were used.

(Reference example 6)
A roll-shaped film (D6) having an average thickness of 75 μm was obtained in the same manner as in Reference Example 5, except that the longitudinal draw ratio was set to 1.56 times and the transverse draw ratio was set to 2 times. Ta.

(Reference example 7)
Pellets of the acrylic resin (B4) obtained in Production Example 4 and the polycarbonate resin (A4) having an aromatic skeleton were extruded into a twin-screw extruder (φ = 37 mm, L/D=34) and kneaded at 260° C. to obtain resin pellets (C3).
The obtained pellets were hot-press molded at 260° C. to obtain an unstretched film having a thickness of about 200 μm. The obtained unstretched film was cut into a size of 96 mm × 96 mm, and a longitudinal stretching rate of 300%/min was applied at a temperature of 145°C using a sequential biaxial stretching machine (X6-S, manufactured by Toyo Seiki Seisakusho Co., Ltd.). A stretched film (D7) having a thickness of 50 μm was obtained by sequentially performing biaxial stretching so that the draw ratio was 2.0 times in the order of the direction (MD direction) and the transverse direction (TD direction) and cooling. However, the film was markedly whitened, and a film that could be evaluated could not be obtained.

Table 5 shows the evaluation results of each example and reference example.

As shown in the above table, a molded article having high transparency, low coloration, and excellent physical properties could be produced without causing whitening or the like, similarly to the above-described Examples.
In particular, the composition (molded body) in the table above contains a relatively large amount of the acrylic resin (B), and maintains excellent transparency and low colorability while maintaining strength (especially, elongation at break, MIT, tear strength, impact strength, etc.) were greatly improved.

ADVANTAGE OF THE INVENTION According to this invention, a novel resin composition etc. can be provided.

Claims (22)

A composition containing a polycarbonate resin (A) containing a polycarbonate resin (A1) having an alicyclic skeleton and an acrylic resin (B) having a ring structure, wherein the proportion of the acrylic resin (B) is the polycarbonate resin (A ) and the acrylic resin (B) in an amount of more than 50% by mass. A composition containing a polycarbonate resin (A) and an acrylic resin (B) having a ring structure, wherein the proportion of the acrylic resin (B) is is more than 50% by mass, and the absolute value of the difference between the refractive index (wavelength 589 nm) _RA of the polycarbonate resin (A) and the refractive index (wavelength 589 nm) RB of the acrylic resin ( _B ) is 0.030 or less. Composition. 3. The composition according to claim 2, wherein the polycarbonate resin (A) comprises a polycarbonate resin (A1) having an alicyclic skeleton. The composition according to claim 1 or 3, wherein the polycarbonate resin (A1) has a structural unit derived from an alicyclic dihydroxy compound. 5. The composition according to claim 1, 3 or 4, wherein the polycarbonate resin (A1) has a structural unit derived from an alicyclic dihydroxy compound represented by the following formula (X).
The composition according to any one of claims 1 to 5, wherein the ratio of the polycarbonate resin (A1) having an alicyclic skeleton to the total polycarbonate resin (A) is 30% by mass or more. The composition according to any one of claims 1 to 6, wherein the polycarbonate resin (A) has a refractive index (wavelength of 589 nm) of 1.540 or less. The composition according to any one of claims 1 to 7, wherein the polycarbonate resin (A) has a glass transition temperature of 90 to 140°C and a melt flow rate of 5 to 25 g/10 minutes at 230°C and a load of 3.8 kg. The composition according to any one of claims 1 to 8, wherein the acrylic resin (B) has at least one ring structure selected from a cyclic imide structure, a cyclic amide structure and a cyclic ester structure. The composition according to any one of claims 1 to 9, wherein the acrylic resin (B) has a cyclic ester structure. The composition according to any one of claims 1 to 10, wherein the acrylic resin (B) has a glass transition temperature of 115°C or higher. The composition according to any one of claims 1 to 11, wherein the acrylic resin (B) has a melt flow rate of 0.5 to 8 g/10 minutes at 230°C and a load of 3.8 kg, and a weight average molecular weight of 50,000 to 200,000. . The composition according to any one of claims 1 to 12, wherein the acrylic resin (B) has a refractive index (wavelength of 589 nm) of 1.492 to 1.510. The composition according to any one of claims 1 to 13, wherein the proportion of acrylic resin (B) is 55 to 95% by mass with respect to the total amount of polycarbonate resin (A) and acrylic resin (B). The polycarbonate resin (A) has a refractive index (wavelength of 589 nm) of 1.520 or less and contains a polycarbonate resin (A1) having an alicyclic skeleton at a rate of 30% by mass or more,
The acrylic resin (B) has a refractive index (wavelength of 589 nm) of 1.494 or higher and a glass transition temperature of 120° C. or higher,
The absolute value of the difference between the refractive index (wavelength 589 nm) _RA of the polycarbonate resin (A) and the refractive index (wavelength 589 nm) _RB of the acrylic resin (B) is 0.020 or less,
The composition according to any one of claims 1 to 14, wherein the proportion of acrylic resin (B) is 60 to 90% by mass with respect to the total amount of polycarbonate resin (A) and acrylic resin (B). The composition of any of claims 1-15, which is not melt-kneaded. A molded article comprising the composition according to any one of claims 1 to 16. 18. The molded article according to claim 17, which is an optical member. 19. The molded article according to claim 17 or 18, which is a decorative film. Total light transmittance of 89% or more, haze of 20% or less, pencil hardness of H or more, elongation at break of 40% or more, folding endurance of 80 times or more, trouser tear strength of 50 mN or more, impact strength of 0.22 J or more , and/or the composition or molded article according to any one of claims 1 to 19, which has a heat shrinkage rate of 0.5% or less. A method for producing a molded article, comprising the step of melt-molding the composition according to any one of claims 1 to 16. 22. The method according to claim 21, wherein at least the polycarbonate resin (A) and the acrylic resin (B) having a ring structure are mixed without being melted to obtain a composition, and the composition is subjected to melt molding.