Polyisocyanate composition, polymerizable composition, resin, molded body, optical element and lens

Abstract

To provide a polyisocyanate composition which can improve transparency of a resin, a polymerizable composition, a resin, a molded body, an optical element and a lens.SOLUTION: A polyisocyanate composition contains polyisocyanate having an isocyanatomethyl group, and a 1-nylon type polymer. A ratio of the mass of an amide bond in the polyisocyanate composition to the mass of an isocyanate group in the polyisocyanate composition is 8,000 ppm or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyisocyanate composition, a polymerizable composition, a resin, a molded article, an optical element, and a lens. [Background technology]

[0002] 2. Description of the Related Art Polyisocyanate compositions have been conventionally known as raw materials for resins used in various industrial products.

[0003] As a polyisocyanate composition, for example, a xylylene diisocyanate composition containing xylylene diisocyanate and dichloromethyl benzyl isocyanate, in which the content of dichloromethyl benzyl isocyanate is 0.6 ppm or more and 60 ppm or less, has been proposed (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 190290 Summary of the Invention [Problem to be solved by the invention]

[0005] For a resin produced from the polyisocyanate composition described in Patent Document 1, there are cases where improvement in transparency is required depending on the purpose and application.

[0006] The present invention provides a polyisocyanate composition, a polymerizable composition, a resin, a molded article, an optical element, and a lens that can improve the transparency of a resin. [Means for solving the problem]

[0007] The present invention [1] relates to a polyisocyanate composition comprising a polyisocyanate having an isocyanatomethyl group and a 1-nylon type polymer, in which the ratio of the mass of amide bonds in the polyisocyanate composition to the mass of isocyanate groups in the polyisocyanate composition is 8000 ppm or less.

[0008] The present invention [2] is a polyisocyanate composition comprising a polyisocyanate having an isocyanatomethyl group and a polyisocyanate having a peak at 1700 cm in an infrared absorption spectrum. -1 over 1710cm -1 and a specific compound having an absorption peak with a peak top in the following range, wherein the ratio of the mass of amide bonds in the polyisocyanate composition calculated from the absorbance at the peak top of the absorption peak to the mass of isocyanate groups in the polyisocyanate composition is 8000 ppm or less.

[0009] The present invention [3] includes the polyisocyanate composition according to the above [1] or [2], in which the ratio is 50 ppm or more.

[0010] The present invention [4] includes the polyisocyanate composition according to any one of the above [1] to [3], wherein the polyisocyanate is xylylene diisocyanate or bis(isocyanatomethyl)bicyclo[2.2.1]heptane. The present invention [5] includes a polymerizable composition containing the polyisocyanate composition according to any one of the above [1] to [4] and an active hydrogen group-containing component.

[0011] The present invention [6] is a process for preparing a mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane-based copolymer, comprising: 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; pentaerythritol tetrakis(2-mercaptoacetate); pentaerythritol tetrakis(3-mercaptopropionate); 2,5-bis(mercaptomethyl)-1,4-dithiane; bis(mercaptomethyl)-1,4-dithiane; The polymerizable composition according to item [5] above contains at least one polythiol selected from the group consisting of 1,2,3-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0012] The present invention [7] includes a resin which is a cured product of the polymerizable composition described in the above [5] or [6].

[0013] The present invention [8] includes a molded article made of the resin described in [7] above.

[0014] The present invention [9] includes an optical element which is the molded article described in [8] above.

[0015] The present invention

[10] includes a lens which is the optical element described in [9] above. Effect of the Invention

[0016] The polyisocyanate composition of the present invention contains specific compounds in specific ratios, and therefore a resin produced from the polyisocyanate composition has excellent transparency.

[0017] The polymerizable composition of the present invention contains the polyisocyanate composition described above. Therefore, a resin produced from the polymerizable composition has excellent transparency.

[0018] The resin of the present invention is a cured product of the above-mentioned polymerizable composition, and therefore has excellent transparency.

[0019] The molded article of the present invention is made of the above-mentioned resin, and therefore has excellent transparency.

[0020] The optical element of the present invention is the above-mentioned molded article, and therefore has excellent transparency.

[0021] The lens of the present invention is the optical element described above, and therefore has excellent transparency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] 1. Polyisocyanate composition The polyisocyanate composition contains, as a main component, a polyisocyanate having an isocyanatomethyl group. An example of a polyisocyanate having an isocyanatomethyl group is a diisocyanate represented by the following chemical formula (1). Chemical formula (1): [ka] In the above chemical formula (1), n ​​is 0 or 1. In the above chemical formula (1), R represents a linear or branched aliphatic group, a cyclic aliphatic group, or an aromatic group. Examples of the linear or branched aliphatic group include linear alkylene groups, such as propylene and butylene groups. In the above chemical formula (1), when R is a linear or branched aliphatic group, the polyisocyanate is an aliphatic diisocyanate. Aliphatic diisocyanates include, for example, pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI). Pentamethylene diisocyanate is a polyisocyanate in which n is 1 and R is a propylene group in the above chemical formula (1).Hexamethylene diisocyanate is a polyisocyanate in which n is 1 and R is a butylene group in the above chemical formula (1). Examples of the cyclic aliphatic group include a cyclohexylene group, a trimethylcyclohexylene group, and a bicyclo[2.2.1]heptylene group. In the above chemical formula (1), when R is a cycloaliphatic group, the polyisocyanate is an alicyclic diisocyanate. Examples of alicyclic diisocyanates include bis(isocyanatomethyl)cyclohexane (BIC), isophorone diisocyanate (IPDI, also known as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), and bis(isocyanatomethyl)bicyclo[2,2,1]heptane (BIBH). Bis(isocyanatomethyl)cyclohexane is a polyisocyanate in which n is 1 and R is a cyclohexylene group in the above chemical formula (1). Isophorone diisocyanate is a polyisocyanate in which n is 0 and R is a trimethylcyclohexylene group in the above chemical formula (1). Bis(isocyanatomethyl)bicyclo[2,2,1]heptane is a polyisocyanate in which n is 1 and R is a bicyclo[2.2.1]heptylene group in the above chemical formula (1). An example of the aromatic group is a phenylene group. In the above formula (1), when R is an aromatic group, the polyisocyanate is an araliphatic diisocyanate. An example of the araliphatic diisocyanate is xylylene diisocyanate (XDI). Xylylene diisocyanate is a polyisocyanate in which n is 1 and R is a phenylene group in the above chemical formula (1). As the polyisocyanate, preferably, alicyclic diisocyanates and araliphatic diisocyanates are used, and more preferably, BIBH and XDI are used.

[0023] Examples of BIBH include 2,5-BIBH and 2,6-BIBH. A polyisocyanate composition containing BIBH as a main component is defined as a BIBH composition. Such BIBH may be contained in one or more kinds in the BIBH composition. Examples of XDI include 1,2-XDI (o-XDI), 1,3-XDI (m-XDI), and 1,4-XDI (p-XDI). A polyisocyanate composition containing XDI as a main component is defined as an XDI composition.

[0024] One or more types of such XDI may be contained in the XDI composition.

[0025] As the XDI, preferably, 1,3-XDI (m-XDI) is used.

[0026] The content (purity) of the polyisocyanate is, for example, 98.00% by mass or more, preferably 99.00% by mass or more, more preferably 99.30% by mass or more, even more preferably 99.60% by mass or more, and for example, 99.95% by mass or less, based on the total mass of the polyisocyanate composition. In other words, the polyisocyanate composition is composed almost entirely of polyisocyanate. The content of the polyisocyanate can be measured by the method described in paragraph

[0377] of WO 2018 / 190290.

[0027] The polyisocyanate composition contains a specific compound as a secondary component.

[0028] In the infrared absorption spectrum, a specific compound has a specific absorption peak due to the carbonyl group in the amide bond. The specific absorption peak is at 1700 cm -1 over 1710cm -1It has a peak top in the following range.

[0029] The polyisocyanate composition may contain other subcomponents in addition to the specific compound.

[0030] When the polyisocyanate composition is an XDI composition, other auxiliary components include, for example, dichloromethylbenzyl diisocyanate (DCI) described in paragraphs

[0028] to

[0030] of WO 2018 / 190290, and monochloromethylbenzyl isocyanate (CBI) described in paragraphs

[0039] to

[0041] of WO 2018 / 190290.

[0031] The DCI content is, for example, 0.1 ppm or more, preferably 0.3 ppm or more, more preferably 0.6 ppm or more, more preferably 1.0 ppm or more, and for example, 60 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, more preferably 20 ppm or less, relative to the total mass of the XDI composition.

[0032] When the content of DCI is within the above range, yellowing and / or clouding of the resin produced from the XDI composition can be suppressed.

[0033] The CBI content is, for example, 0.2 ppm or more, preferably 6 ppm or more, more preferably 100 ppm or more, and for example, 5000 ppm or less, preferably 4000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1600 ppm or less, and particularly preferably 1000 ppm or less, relative to the total mass of the XDI composition.

[0034] In addition, the content of CBI is, for example, 2 times or more, preferably 10 times or more, more preferably 20 times or more, and for example, 800 times or less, preferably 300 times or less, more preferably 50 times or less, relative to the content of DCI.

[0035] If the CBI content is within the above range, yellowing of the resin produced from the XDI composition can be reliably suppressed. In particular, if the CBI content is equal to or less than the above upper limit, yellowing of the resin produced from the XDI composition can be reliably suppressed, and the urethane reaction during the production of the resin can proceed smoothly, thereby reliably improving the mechanical properties of the resin.

[0036] The DCI content and the CBI content can be measured by the method described in the examples of WO 2018 / 190290.

[0037] Specific compounds include, for example, 1-nylon type polymers.

[0038] As described in "The Homopolymerization of Monoisocyanates" on page 866 of the Journal of the American Chemical Society Vol. 82 (1960), "1-nylon type polymer" is a polymer formed by polymerization of isocyanate monomers, and has amide bonds resulting from the reaction between isocyanate groups. 1-nylon type polymers have a linear main chain with successive amide bonds. 1-nylon type polymers do not contain isocyanurate.

[0039] Examples of the 1-nylon type polymer include a homopolymer of polyisocyanate. Examples of the homopolymer of polyisocyanate include a polymer represented by the following chemical formula (2) and a polymer represented by the following chemical formula (3).

[0040] Chemical formula (2):

[0041] [ka]

[0042] In the above chemical formula (2), m is an integer of 2 or more. In the above chemical formula (2), R and n are the same as R and n in the above chemical formula (1).

[0043] Chemical formula (3):

[0044] [ka]

[0045] In the above chemical formula (3), m and p are integers of 2 or more. p may be a number different from m. In the above chemical formula (3), R and n are the same as R and n in the above chemical formula (1).

[0046] In addition, when the polyisocyanate composition is an XDI composition, the XDI composition is produced by the production method described below, and contains CBI and DCI as minor components, the 1-nylon type polymer may be a homopolymer of the above-mentioned XDI, or a copolymer having at least two of a structural unit derived from XDI (see chemical formula (4) below), a structural unit derived from CBI (see chemical formula (5) below), and a structural unit derived from DCI (see chemical formula (6) below).

[0047] Chemical formula (4):

[0048] [ka]

[0049] Chemical formula (5):

[0050] [ka]

[0051] Chemical formula (6):

[0052] [ka]

[0053] The ratio (B / A) of the mass (B) of the amide bond in the XDI composition to the mass (A) of the isocyanate group in the polyisocyanate composition is, for example, 50 ppm or more, preferably 100 ppm or more, more preferably 150 ppm or more, more preferably 200 ppm or more, more preferably 500 ppm or more, more preferably 1000 ppm or more, and more preferably 1500 ppm or more.

[0054] Specifically, the ratio (B / A) is expressed by the following formula, as described in the Examples below.

[0055] Formula: Proportion (B / A) = Mass (B) / Mass (A) x 1000000 Mass (A) is the mass of the isocyanate group in the polyisocyanate composition, assuming that the entire polyisocyanate composition is polyisocyanate. Mass (A) is calculated from the mass of the sampled polyisocyanate, the molecular weight of the polyisocyanate, and the molecular weight of the isocyanate group. Mass (A) is calculated by the calculation method described in the examples below.

[0056] Mass (B) is calculated from the absorbance at the peak top of the specific absorption peak described above. Mass (B) is calculated by the calculation method described in the Examples described later. In the Examples described later, mass (B) is calculated by multiplying the absorbance at the peak top of the absorption peak by the absorption coefficient (absorption coefficient of tris(2,3-dibromopropyl)isocyanurate). In other words, mass (B) is a converted value based on the absorption coefficient of tris(2,3-dibromopropyl)isocyanurate.

[0057] When the ratio (B / A) is equal to or more than the lower limit, the haze value of the cured product described below can be reduced, and therefore the transparency of the cured product can be improved.

[0058] The haze value can be measured by the method described in the Examples section below.

[0059] The ratio (B / A) is 8000 ppm or less, preferably 7500 ppm or less, more preferably 5000 ppm or less, and more preferably 4000 ppm or less.

[0060] When the ratio (B / A) is equal to or less than the upper limit, the haze value and the devitrification degree of the cured product can be reduced, thereby improving the transparency of the cured product.

[0061] The devitrification degree can be measured by the method described in the examples below.

[0062] 2. Method for producing polyisocyanate composition Next, a method for producing the polyisocyanate composition will be described.

[0063] The method for producing the polyisocyanate composition includes a step of producing a reaction mass (pre-purification composition), a step of purifying the reaction mass, and a step of mixing air, if necessary, to adjust the content ratio of the polyisocyanate and the specific compound to be within the above-mentioned range.

[0064] When the polyisocyanate composition is an XDI composition, the reaction mass is produced, for example, by the production method described in paragraphs

[0054] to

[0110] of International Publication No. 2018 / 190290. In detail, the reaction mass is produced, for example, by mixing xylylenediamine and hydrogen chloride to form xylylenediamine hydrochloride, and then reacting the hydrochloride with carbonyl chloride (phosgene) (amine hydrochloride phosgenation method).

[0065] In the following, xylylenediamine is referred to as XDA. Examples of XDA include 1,2-XDA (o-XDA), 1,3-XDA (m-XDA), and 1,4-XDA (p-XDA), and preferably 1,3-XDA (m-XDA).

[0066] In the salt formation step of forming XDA hydrochloride, for example, XDA and hydrogen chloride are mixed in the presence of an inert solvent to produce XDA hydrochloride (salt formation).

[0067] Examples of the inert solvent include the inert solvents described in paragraph

[0059] of International Publication No. 2018 / 190290. The inert solvent can be used alone or in combination of two or more. Among the inert solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

[0068] Hydrogen chloride gas is then supplied to the amine solution in which XDA is dissolved in an inert solvent, and the hydrogen chloride gas and the amine solution are then mixed by stirring.

[0069] The mass ratio of XDA to the sum of the masses of XDA and the inert solvent (total amine concentration) is, for example, 3 mass% or more, preferably 5 mass% or more, and for example, 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less.

[0070] The supply ratio of hydrogen chloride is, for example, 2 mol or more and, for example, 10 mol or less, preferably 6 mol or less, and more preferably 4 mol or less, relative to 1 mol of XDA.

[0071] The salt formation temperature in the salt formation step is, for example, 30° C. or more, preferably 50° C. or more, and for example, 160° C. or less, preferably 150° C. or less. The salt formation pressure (gauge pressure) in the salt formation step is, for example, atmospheric pressure (0 MPaG) or more, preferably 0.01 MPaG or more, and for example, 1.0 MPaG or less, preferably 0.5 MPaG or less.

[0072] As a result, XDA hydrochloride is produced from XDA and hydrogen chloride (hydrochloridation reaction), and a slurry containing XDA hydrochloride is produced.

[0073] Next, carbonyl chloride is supplied to the slurry containing XDA hydrochloride to react with the carbonyl chloride (isocyanation reaction, phosgenation).

[0074] The supply ratio of carbonyl chloride is, relative to 1 mole of XDA hydrochloride, for example, 4 moles or more, preferably 5 moles or more, more preferably 6 moles or more, and for example, 50 moles or less, preferably 40 moles or less, more preferably 30 moles or less.

[0075] The reaction time of the isocyanation step is, for example, 4 hours or more, preferably 6 hours or more, and for example, 25 hours or less, preferably 20 hours or less, more preferably 15 hours or less.

[0076] The reaction temperature in the isocyanation step is, for example, 90°C or more, preferably 100°C or more, more preferably 110°C or more, and for example, 190°C or less, preferably 180°C or less, more preferably 160°C or less.

[0077] The reaction pressure (gauge pressure) in the isocyanation step exceeds atmospheric pressure (0 MPaG), and is preferably 0.0005 MPaG or more, more preferably 0.001 MPaG or more, even more preferably 0.003 MPaG or more, particularly preferably 0.01 MPaG (10 kPaG) or more, particularly preferably 0.02 MPaG (20 kPaG) or more, most preferably 0.03 MPaG (30 kPaG) or more, and is, for example, 0.6 MPaG or less, preferably 0.4 MPaG or less, more preferably 0.2 MPaG or less.

[0078] The isocyanation step is preferably carried out in a continuous manner, that is, the slurry (XDA hydrochloride) produced in the stirring tank is continuously transferred from the stirring tank to a reaction tank separate from the stirring tank, and the reaction liquid (reaction mass) is continuously removed from the reaction tank while the XDA hydrochloride is reacted with carbonyl chloride in the reaction tank.

[0079] This causes XDA hydrochloride to react with carbonyl chloride to produce XDI as the main component.

[0080] Next, if necessary, the reaction liquid (reaction mixture) is subjected to a degassing step, a desolvation step, and a detarring step. In the degassing step, excess carbonyl chloride and by-product gases such as hydrogen chloride are removed from the reaction liquid (reaction mixture) using a known degassing tower. In the desolvation step, the inert solvent is distilled off from the reaction liquid using a known distillation tower. In the detarring step, tar components are removed from the reaction liquid using a known detarring device.

[0081] In this manner, a reaction mass containing XDI is produced.

[0082] The content of XDI in the reaction mass is, for example, 80.0 mass% or more, preferably 90.0 mass% or more, more preferably 95.0 mass% or more, and for example, 99.0 mass% or less, preferably 98.5 mass% or less, more preferably 98.0 mass% or less. In addition, when the polyisocyanate composition is a BIBH composition, it can be produced by the hydrochloride method, similarly to the XDI composition. Specifically, when the polyisocyanate composition is a BIBH composition, the reaction mass is produced, for example, by the production method described in paragraph

[0072] of International Publication No. 2007 / 010996.

[0083] The reaction mass is then purified.

[0084] An example of a method for purifying the reaction mass is distillation. In order to purify the reaction mass by distillation, for example, low boiling matters (low boiling point components) are distilled off from the reaction mass by distillation, and the reaction mass after removing the low boiling matters is rectified.

[0085] In the low boiling point removal step, for example, the reaction mass is distilled in a low boiling point removal tower to remove the low boiling points.

[0086] Examples of the low boiling tower include a plate tower and a packed tower, and preferably a packed tower. The theoretical number of stages of the low boiling tower is, for example, 3 or more, preferably 5 or more, more preferably 7 or more, and for example, 40 or less, preferably 20 or less, more preferably 15 or less.

[0087] The bottom temperature of the low boiling removal tower is, for example, 130°C or more, preferably 140°C or more, more preferably 150°C or more, and for example, 200°C or less, preferably 190°C or less, more preferably 180°C or less.

[0088] The top temperature of the low boiling removal tower is, for example, 90°C or more, preferably 100°C or more, more preferably 110°C or more, and for example, 160°C or less, preferably 150°C or less, more preferably 140°C or less.

[0089] The pressure at the top of the low boiling separation tower is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, and for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0090] The top reflux ratio of the low boiling separation tower is, for example, 1 or more, preferably 5 or more, more preferably 10 or more, and for example, 80 or less, preferably 60 or less, more preferably 50 or less.

[0091] The residence time in the low boiling removal tower is, for example, 0.1 hours or more, preferably 0.2 hours or more, more preferably 0.3 hours or more, and for example, 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

[0092] From this, low boiling matters are distilled off, and the low boiling matter is removed and obtained as the bottoms.

[0093] Next, in the rectification step, for example, the low boiling mass is distilled in a rectification column to extract a fraction.

[0094] The rectification tower may, for example, be a plate tower or a packed tower, preferably a packed tower. The number of theoretical plates of the rectification tower is, for example, 1 or more, and, for example, 20 or less, preferably 10 or less, more preferably 5 or less.

[0095] The bottom temperature of the rectification column is, for example, 120° C. or more, preferably 130° C. or more, more preferably 140° C. or more, and for example, 190° C. or less, preferably 180° C. or less, more preferably 170° C. or less.

[0096] The top temperature of the rectification column is, for example, 90°C or more, preferably 110°C or more, more preferably 130°C or more, and for example, 180°C or less, preferably 170°C or less, more preferably 160°C or less.

[0097] The top pressure of the rectification column is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, and for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0098] The column top reflux ratio of the rectification column is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, and for example, 50 or less, preferably 20 or less, more preferably 10 or less.

[0099] The residence time in the rectification column is, for example, 0.2 hours or more, preferably 0.5 hours or more, more preferably 1.0 hour or more, and for example, 20 hours or less, preferably 10 hours or less.

[0100] As a result of the above, the polyisocyanate composition is taken out as a distillate.

[0101] Next, if necessary, air is mixed into the extracted polyisocyanate composition to adjust the content ratio of the polyisocyanate and the specific compound to be within the above range. In some cases, the content ratio of the specific compound can be adjusted to be within the above range by reducing the amount of the specific compound in the polyisocyanate composition through filtering the polyisocyanate composition.

[0102] The air is preferably dry air.

[0103] The relative humidity of the air is, for example, 95% or less, preferably 85% or less. There is no lower limit for the relative humidity of the air. The relative humidity of the air is, for example, 15% or more.

[0104] The air temperature is, for example, 5°C or more, preferably 10°C or more, and for example, 30°C or less, preferably 25°C or less.

[0105] An example of a method for mixing air into the XDI composition is blowing air into the XDI composition through a glass air blowing tube.

[0106] <Action and effect> The polyisocyanate composition of the present invention contains specific compounds in specific ratios.

[0107] Specifically, the specific compound is a 1-nylon type polymer, and has an infrared absorption spectrum of 1700 cm -1 over 1710cm -1 It has an absorption peak with a peak top in the following range.

[0108] The ratio of the mass of amide bonds in the polyisocyanate composition to the mass of isocyanate groups in the polyisocyanate composition is 8000 ppm or less.

[0109] Therefore, a resin produced from the above-mentioned polyisocyanate composition has excellent transparency.

[0110] 3. Polymerizable composition The polyisocyanate composition described above is used as a raw material for resins, and is particularly suitable for use as a raw material for optical materials. In other words, the polyisocyanate composition is preferably contained in a polymerizable composition as an isocyanate component.

[0111] The polymerizable composition includes an isocyanate component and an active hydrogen group-containing component.

[0112] The isocyanate component contains, and preferably consists of, a polyisocyanate composition.

[0113] Examples of the active hydrogen group-containing component include a polyol component, a polythiol component, and a polyamine component.

[0114] The active hydrogen group-containing component can be used alone or in combination of two or more kinds.

[0115] Among the active hydrogen group-containing components, polythiol components are preferable from the viewpoint of optical properties, for example.

[0116] Examples of the polythiol component include an aliphatic polythiol compound, an aromatic polythiol compound, and a heterocyclic polythiol compound.

[0117] Examples of the aliphatic polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), ester), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-Dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters with thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercapto propionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane.

[0118] Examples of aromatic polythiol compounds include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol.

[0119] Heterocyclic polythiol compounds include, for example, 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, and bismuthiol.

[0120] Such polythiol components can be used alone or in combination of two or more kinds.

[0121] As the polythiol component, preferably, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptomethyl)-1,4-dithiane,

[0043] At least one selected from the group consisting of 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0122] 3. Resin The resin is produced by reacting the above-mentioned isocyanate component with the above-mentioned active hydrogen group-containing component. In other words, the resin is a cured product of the polymerizable composition. The resin has excellent transparency and is therefore suitable as an optical material.

[0123] Specifically, the haze value of the resin is, for example, 0.70 or less, preferably 0.60 or less, more preferably 0.50 or less, more preferably 0.40 or less, and more preferably 0.35 or less. When the haze value is equal to or less than the above upper limit, the resin has excellent transparency.

[0124] The lower limit of the haze value of the resin is not limited, and the haze value of the resin is, for example, 0.10 or more.

[0125] The devitrification degree of the resin is, for example, not more than 30, preferably not more than 25, more preferably not more than 22, and more preferably not more than 21. When the devitrification degree is not more than the above upper limit, the resin has excellent transparency.

[0126] The lower limit of the devitrification degree of the resin is not limited, and the devitrification degree of the resin is, for example, 10 or more.

[0127] The resin is preferably molded by a known molding method. That is, the molded article is made of a resin. The molded article is suitable as an optical component. An example of the molded article of the resin is an optical element.

[0128] The optical element includes, for example, a lens, a sheet, and a film, and preferably includes a lens.

[0129] The lens is produced, for example, by reacting the above-mentioned polyisocyanate composition with the above-mentioned polythiol component. In producing the lens, for example, a casting method can be adopted.

[0130] Examples of lenses include clear lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0131] <Action and effect> The above-mentioned resin, molded article, optical element and lens contain a cured product of the above-mentioned polymerizable composition, and therefore the resin, molded article, optical element and lens have excellent transparency.

[0132] The polyisocyanate composition described above can also be used as a raw material for coatings (for example, paints and adhesives). In this case, the polyisocyanate composition is modified by a known method as necessary and is contained as an isocyanate component in a polymerizable composition for coating.

[0133] The xylylene diisocyanate modified composition (hereinafter referred to as the polyisocyanate modified composition) is produced by modifying the above-mentioned polyisocyanate composition, and contains at least one of the following functional groups (a) to (i). (a) an isocyanurate group, (b) an allophanate group; (c) a biuret group, (d) a urethane group, (e) a urea group, (f) an iminooxadiazinedione group, (g) a uretdione group, (h) a uretonimine group, (i) A carbodiimide group.

[0134] More specifically, the polyisocyanate modified composition containing the functional group (isocyanurate group) of (a) above contains a trimer of polyisocyanate, and can be obtained, for example, by adding a known isocyanuration catalyst to a polyisocyanate monomer composition, reacting the composition, and isocyanurating (e.g., trimerizing) the polyisocyanate.

[0135] The polyisocyanate-modified composition containing the functional group (allophanate group) of (b) above contains an allophanate-modified polyisocyanate, and can be obtained, for example, by reacting a polyisocyanate monomer composition with a monohydric alcohol or a dihydric alcohol, and then adding a known allophanate-forming catalyst to further react the mixture.

[0136] The polyisocyanate-modified composition containing the functional group (biuret group) of (c) above contains a biuret-modified polyisocyanate, and can be obtained, for example, by reacting a polyisocyanate monomer composition with water or a secondary amine, and then adding a known biuret catalyst to further react the mixture.

[0137] The polyisocyanate-modified composition containing the functional group (urethane group) of (d) above contains a polyol-modified polyisocyanate, and can be obtained, for example, by reacting a polyisocyanate monomer composition with a low-molecular-weight polyol (e.g., trimethylolpropane).

[0138] The polyisocyanate-modified composition containing the functional group (urea group) of (e) above contains a polyamine-modified polyisocyanate, and can be obtained, for example, by reacting a polyisocyanate monomer composition with a polyamine.

[0139] The polyisocyanate modified composition containing the functional group (iminooxadiazinedione group) of (f) above contains an iminooxadiazinedione modified polyisocyanate (asymmetric trimer), and can be obtained, for example, by reacting a polyisocyanate composition in the presence of a known iminooxadiazinedione-forming catalyst to convert the polyisocyanate into an iminooxadiazinedione (e.g., trimerization).

[0140] The polyisocyanate modified composition containing the functional group (uretdione group) of (g) contains a uretdione modified polyisocyanate, and can be obtained, for example, by heating the polyisocyanate composition at about 90°C to 200°C, or by reacting in the presence of a known uretdione-forming catalyst to uretdioneize (e.g., dimerize) the polyisocyanate.

[0141] The polyisocyanate modified composition containing the functional group (uretonimine group) of (h) above contains a uretonimine modified polyisocyanate, and can be obtained, for example, by reacting a polyisocyanate composition in the presence of a known carbodiimide catalyst to form a carbodiimide group, and then adding a polyisocyanate to the carbodiimide group.

[0142] The polyisocyanate-modified composition containing the functional group (carbodiimide group) described above (i) contains a carbodiimide-modified polyisocyanate, and can be obtained, for example, by reacting a polyisocyanate composition in the presence of a known carbodiimide catalyst.

[0143] The polyisocyanate modified composition may contain at least one of the functional groups (a) to (i) above, and may contain two or more of them. The polyisocyanate modified composition may be used alone or in combination of two or more of them.

[0144] The polymerizable composition for coating is, for example, a two-component curable resin raw material, and contains an agent A as a curing agent and an agent B as a main agent.

[0145] The component A includes, for example, the polyisocyanate-modified composition described above, and the component B includes, for example, a polyol component.

[0146] A coating formed from such a polymerizable composition for coating also has excellent transparency. EXAMPLES

[0147] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numerical values ​​defined as "less than or equal to" or "less than") or lower limit values ​​(numerical values ​​defined as "more than or equal to" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention". In addition, "parts" and "%" are based on mass unless otherwise specified.

[0148] 1. Preparation of XDI composition The XDI composition was produced by the method described in WO 2018-190290.

[0149] Next, a predetermined amount of air was mixed into the obtained XDI composition to adjust the "ratio of amide bonds in the XDI composition to the mass of isocyanate groups in the XDI composition" to the ratio shown in Table 1.

[0150] Specifically, dry air dried by passing it through an anhydrous calcium chloride tube was blown into the XDI composition filled in a glass container through a glass blowing tube in an atmosphere of 25°C, thereby mixing a predetermined amount of air into the XDI composition.

[0151] As a result, the XDI compositions of Examples 1 to 7 and Comparative Example 1 were obtained.

[0152] In Table 1, "the ratio of the mass of amide bonds in the XDI composition to the mass of isocyanate groups in the XDI composition" is represented as "1-nylon / NCO." 2. Preparation of BIBH composition A BIBH composition was prepared according to the method described in Example 4 of WO 2007-010996. Next, a predetermined amount of air was mixed into the obtained BIBH composition to adjust the "ratio of amide bonds in the BIBH composition to the mass of isocyanate groups in the BIBH composition" to the ratio shown in Table 2. Specifically, dry air, which had been dried by passing it through an anhydrous calcium chloride tube, was blown into the BIBH composition filled in a glass container through a glass blowing tube in an atmosphere of 25°C, thereby mixing a predetermined amount of air into the BIBH composition. As a result, the BIBH compositions of Examples 8 to 14 and Comparative Examples 2 and 3 were obtained. In Table 2, "the ratio of the mass of amide bonds in the BIBH composition to the mass of isocyanate groups in the BIBH composition" is represented as "1-nylon / NCO."

[0153] 2. Manufacturing of plastic lenses (1) Manufacturing of plastic lenses using XDI compositions 50.8 parts by mass of the XDI composition "1-nylon / NCO" shown in Table 1 was mixed and dissolved at 20°C with 0.01 parts by mass of dimethyltin dichloride as a curing catalyst, 0.10 parts by mass of Zerec UN (product name, Stepan Corporation; acidic phosphate ester), and 1.5 parts by mass of Biosorb 583 (Sakai Chemical Industry Co., Ltd.; ultraviolet absorber) to obtain mixed solution 1.

[0154] Next, 49.2 parts by mass of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was uniformly mixed into the mixed liquid 1 to obtain a mixed liquid 2.

[0155] Mixture 2 was degassed at 600 Pa for 1 hour, and then filtered through a 1 μm Teflon (registered trademark) filter.

[0156] Next, the filtered mixed liquid 2 was poured into a mold consisting of a glass mold and tape.

[0157] Next, the mold into which the mixed liquid 2 had been poured was placed in an oven, the temperature was raised from 25° C. to 120° C., and polymerization was carried out at 120° C. for 24 hours.

[0158] After the polymerization was completed, the mold was removed from the oven, the polymer was released from the mold, and the resulting polymer was annealed at 120° C. for 1 hour.

[0159] As a result, cured products of Examples 1 to 7 and Comparative Example 1 were obtained. (2) Manufacturing of plastic lenses using BIBH composition 50.6 parts by mass of the BIBH composition "1-nylon / NCO" shown in Table 2 was mixed and dissolved at 20°C with 0.02 parts by mass of dimethyltin dichloride as a curing catalyst and 0.10 parts by mass of Zerec UN (product name: Stepan Corporation product; acidic phosphate ester) to obtain mixed solution 1. Next, 25.5 parts by mass of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of a polythiol composition mainly composed of pentaerythritol tetrakis(3-mercaptopropionate) were added to mixed solution 1, and the mixture was stirred and mixed at 20°C to obtain mixed solution 2, which is a transparent homogeneous solution. The mixed liquid 2 was degassed at 600 Pa for 1 hour. Next, the mixed liquid 2 was poured into a mold consisting of a glass mold and tape. Next, the mold into which the mixed liquid 2 had been poured was placed in an oven, the temperature was raised from 25° C. to 120° C., and polymerization was carried out at 120° C. for 24 hours. After the polymerization was completed, the mold was removed from the oven, the polymer was released from the mold, and the resulting polymer was annealed at 120° C. for 1 hour. As a result, cured products of Examples 8 to 14 and Comparative Examples 2 and 3 were obtained.

[0160] 3.Measurement method (1) 1-Nylon / NCO A calibration curve was prepared using tris(2,3-dibromopropyl)isocyanurate (Tokyo Chemical Industry Co., Ltd.).

[0161] Tris(2,3-dibromopropyl)isocyanurate is an isocyanurate that is a carbonyl group absorbance peak (1700 cm) in 1-nylon type polymers of XDI or BIBH. -1 ~1710cm -1 ), close to the carbonyl group absorption peak (1694 cm -1 Therefore, a calibration curve prepared using tris(2,3-dibromopropyl)isocyanurate was used as the calibration curve for quantifying 1-nylon type polymers of XDI or BIBH.

[0162] For each Example and Comparative Example, a predetermined amount (mg) of the XDI composition or BIBH composition was sampled and diluted with chloroform, and the infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, Model 61000) with a 2.0 mm thick NaCl cell.

[0163] In all the infrared absorption spectra of each Example and Comparative Example, -1 over 1710cm -1 Absorption peaks appeared having peak tops in the following ranges:

[0164] The mass (B) of the amide bond in the XDI composition or BIBH composition was calculated by multiplying the absorbance at the peak top of the absorption peak by the slope of the calibration curve (i.e., the extinction coefficient). In other words, the mass (B) is a converted value based on the extinction coefficient of tris(2,3-dibromopropyl)isocyanurate.

[0165] In addition, 1-nylon / NCO (ppm) was calculated from the following formula (1).

[0166] Formula (1): 1-nylon / NCO (ppm) = mass of amide bonds in the XDI composition or BIBH composition (B) / mass of isocyanate groups in the XDI composition or BIBH composition (A) × 1,000,000 The mass (A) of the isocyanate group in the XDI composition is calculated by the following formula (2): The mass (A) of the isocyanate group in the BIBH composition is calculated by the following formula (3).

[0167] Formula (2): Mass of isocyanate groups in the XDI composition (A) = amount of sampled XDI composition (mg) × (42 × 2 / 188.2) In the above formula (2), "42" is the molecular weight of the isocyanate group, and "188.2" is the molecular weight of XDI. Formula (3): Mass of isocyanate groups in the BIBH composition (A) = Amount of sampled BIBH composition (mg) × (42 × 2 / 206.25) In the above formula (3), "42" is the molecular weight of the isocyanate group, and "206.25" is the molecular weight of BIBH.

[0168] The results are shown in Tables 1 and 2.

[0169] (2) Haze value The cured products of Examples 1 to 7 and Comparative Example 1 were molded into 2.5 mm thick plates, and the cured products of Examples 8 to 14 and Comparative Examples 2 and 3 were molded into 2.0 mm thick plates, and the haze values ​​were measured using a haze meter (model: NDH 2000) manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the haze value, the more transparent the lens. The results are shown in Tables 1 and 2.

[0170] (3)Device clarity The cured products of Examples 1 to 7 and Comparative Example 1 were molded into disk-shaped plastic lenses (thickness 9 mm, diameter 75 mm).

[0171] Next, light from a light source (Hayashi Lepic's Luminar Ace LA-150A) was passed through the lens.

[0172] An image of the light transmitted through the disk lens was captured in an image processing device (manufactured by Ube Information Systems Co., Ltd.), and the captured image was subjected to shading processing.

[0173] The degree of shading in the processed image was quantified for each pixel, and the average value of the numerical values ​​of the degree of shading for each pixel was calculated. The average value obtained is the degree of devitrification of the lens. The smaller the degree of devitrification, the more transparent the lens is. The results are shown in Table 1. (4) Yellow Index Value (YI Value) The cured products of Examples 8 to 14 and Comparative Examples 2 and 3 were molded into disk-shaped (thickness 9 mm, diameter 75 mm) plastic lenses (optical elements). The YI value of the transmission of the obtained plastic lens was measured using a spectrophotometer CM-5 (manufactured by Konica Minolta). The smaller the YI value, the better the hue of the plastic lens, and the larger the YI value, the worse the hue. The results are shown in Table 2.

[0174] [Table 1] [Table 2] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial Applicability]

[0175] The polyisocyanate composition, polymerizable composition, resin and molded article of the present invention are used for optical elements such as lenses, sheets and films.

Claims

1. A polyisocyanate composition for use in producing an optical material, comprising: a polyisocyanate having an isocyanatomethyl group; At least one of monochloromethyl benzyl isocyanate and dichloromethyl benzyl isocyanate; 1-Nylon type polymers and Contains the polyisocyanate is xylylene diisocyanate or bis(isocyanatomethyl)bicyclo[2.2.1]heptane; A polyisocyanate composition, wherein the ratio of the mass of amide bonds in the polyisocyanate composition to the mass of isocyanate groups in the polyisocyanate composition is 8000 ppm or less.

2. A polyisocyanate composition for use in producing an optical material, comprising: a polyisocyanate having an isocyanatomethyl group; At least one of monochloromethyl benzyl isocyanate and dichloromethyl benzyl isocyanate; In the infrared absorption spectrum, 1700 cm －１ 1710cm or more －１ A specific compound having an absorption peak with a peak top in the following range: Contains the polyisocyanate is xylylene diisocyanate or bis(isocyanatomethyl)bicyclo[2.2.1]heptane; A polyisocyanate composition, wherein the ratio of the mass of amide bonds in the polyisocyanate composition calculated from the absorbance at the peak top of the absorption peak to the mass of isocyanate groups in the polyisocyanate composition is 8000 ppm or less.

3. The polyisocyanate composition according to claim 1 or 2, wherein the mass ratio of the amide bond in the polyisocyanate composition is 50 ppm or more.

4. The polyisocyanate composition according to claim 1 or 2; Active hydrogen group-containing component A polymerizable composition comprising:

5. The active hydrogen group-containing component is selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, ...

5. The polymerizable composition according to claim 4, comprising at least one polythiol selected from the group consisting of 1,2,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

6. A resin which is a cured product of the polymerizable composition according to claim 4.

7. A molded article made of the resin according to claim 6.

8. An optical element, which is the molded article according to claim 7 .

9. A lens, which is the optical element according to claim 8.

10. Use of the polyisocyanate composition according to claim 1 or 2 for the production of optical materials.