Curable compositions for semiconductor devices, cured products for semiconductor devices, and semiconductor devices

Abstract

To provide a curable composition which gives a cured product having excellent moisture barrier property and transparency and capable of reducing tack and shrinkage due to curing.SOLUTION: There is provided a curable composition which comprises a component A: a polymer having hydrophobicity and a (meth)acryloyl group, a component B: a monomer having hydrophobicity and one (meth)acryloyl group, a component C: a monomer having hydrophobicity and two (meth)acryloyl groups and a component D: a photoradical polymerization initiator, wherein the content of the component A is larger than the total content of the component B and the component C and the value of the content of the component B / the content of the component C is 0.5 to 4.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a curable composition. [Background technology]

[0002] A technique for applying curable compositions that harden upon irradiation with active energy rays as encapsulants for organic semiconductor devices such as flexible OLEDs is conventionally known (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2016-135860 [Overview of the project] [Problems that the invention aims to solve]

[0004] The cured products obtained from the curable compositions used in the above-mentioned applications are required to have properties such as moisture barrier properties, transparency, reduced tack (reduced stickiness), and reduced shrinkage during curing. The inventors of this invention have investigated and found that the technology described in Patent Document 1 has room for improvement in terms of transparency and reduced tack among the above-mentioned properties.

[0005] One aspect of the present invention aims to provide a curable composition that yields a cured product with excellent moisture barrier properties and transparency, and reduced tack and shrinkage associated with curing. [Means for solving the problem]

[0006] The present invention includes the following embodiments. <1> A curable composition containing the following components A to D, Component A: A hydrophobic polymer having (meth)acryloyl groups. Component B: A monomer that is hydrophobic and has one (meth)acryloyl group. Component C: A monomer that is hydrophobic and has two (meth)acryloyl groups. Component D: Photoradical polymerization initiator The amount of component A is greater than the total amount of components B and C. The ratio of the content of component B to the content of component C is between 0.5 and 4.0. Curable composition. <2> The main chain of component A is polybutadiene or hydrogenated polybutadiene. <1> The curable composition described above. <3> The glass transition temperature of the monomer B described above, when used as a homopolymer, is 0°C or higher. <1> or <2> The curable composition described above. <4> The glass transition temperature of the above-mentioned component C monomer when it is a homopolymer is 0°C or higher. <1> ~ <3> A curable composition as described in any of the following. <5> It also contains the following ingredient E: Component E: Leveling agent The above component E is one or more selected from the group consisting of acrylic leveling agents and silicone leveling agents. <1> ~ <4> A curable composition as described in any of the following. <6> The above component D is an α-hydroxyketone type photoradical polymerization initiator. <1> ~ <5> A curable composition as described in any of the following. <7> Assuming the total weight of the curable composition is 100% by weight, The content of component A mentioned above is 40-70% by weight. The content of component B mentioned above is 10-40% by weight. The content of component C mentioned above is 10-20% by weight. <1> ~ <6> A curable composition as described in any of the following. <8> <1> ~ <7> A cured product obtained by curing any of the curable compositions described in the following. <9> <8> A semiconductor device comprising the cured material described above.

Advantages of the Invention

[0007] According to one aspect of the present invention, there is provided a curable composition that gives a cured product excellent in moisture barrier properties and transparency and having reduced shrinkage associated with tack and curing.

Mode for Carrying Out the Invention

[0008] Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited thereto.

[0009] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less". In this specification, the "(meth)acryloyl group" means an "acryloyl group" and / or a "methacryloyl group".

[0010] The curable composition according to one aspect of the present invention contains the following components A to D and contains the following component E as an optional component. Hereinafter, each component will be described in detail. Component A: A polymer having a hydrophobicity and a (meth)acryloyl group Component B: A monomer having a hydrophobicity and one (meth)acryloyl group Component C: A monomer having a hydrophobicity and two (meth)acryloyl groups Component D: A photo radical polymerization initiator Component E: A leveling agent

[0011] <​​​​​​​​The specific structure of component A is not limited as long as it is a polymer having a (meth)acryloyl group in its molecule. The (meth)acryloyl group may be introduced at the end of the molecular chain, at the terminal portion of the molecular chain, or at the central portion of the molecular chain. "Terminal portion of the molecular chain" refers to, for example, a region that is within 20% or 10% of the molecular chain when counting from the end of the molecular chain, with the total number of units in the polymer being 100%. "Central portion of the molecular chain" refers to, for example, a region of the polymer excluding the terminal portion of the molecular chain.

[0013] The lower limit of the number of (meth)acryloyl groups contained in component A is preferably one or more per molecule on average, and more preferably two or more. The upper limit of the number of (meth)acryloyl groups contained in component A may be, for example, four or less. If the number of (meth)acryloyl groups per molecule is one or more, the tackiness of the cured product is reduced. If the number of (meth)acryloyl groups is within the above range, a cured product with appropriate strength can be obtained.

[0014] In one embodiment, the (meth)acryloyl group has the structure of the following formula (1). In the formula, R 1 This is either a hydrogen atom or a methyl group. Formula (1) -C(=O)C(R 1 )=CH2

[0015] In one embodiment, the (meth)acryloyl group is bonded to the main chain via a spacer. The specific structure of the spacer is well known to those skilled in the art. The spacer (and the bond between the (meth)acryloyl group and the spacer) may have a urethane bond, an ester bond, or a combination thereof. Of these, the structure having a urethane bond is advantageous in that it is resistant to hydrolysis.

[0016] The composition and structure of the main chain are not particularly limited. The main chain may be a homopolymer or a copolymer. Examples of copolymers include random copolymers, block copolymers (diblock copolymers, triblock copolymers, multiblock copolymers of three or more blocks, etc.), and gradient copolymers. The main chain may be linear or non-linear. Examples of branched polymers include graft polymers, star polymers, and cyclic polymers.

[0017] The monomers constituting the main chain are not particularly limited. Examples of monomers include diene monomers and olefin monomers. Examples of diene monomers include butadiene and isoprene. An example of an olefin monomer is isobutene. The main chain may also be hydrogenated. In one embodiment, the main chain is polybutadiene or hydrogenated polybutadiene. When component A having such a main chain is incorporated, the moisture barrier properties tend to improve.

[0018] Component A may be a commercially available polymer. Examples of such polymers include CN9014 (Sartomer, hydrogenated polybutadiene main chain), TEAI-1000 (Nippon Soda Co., Ltd., hydrogenated polybutadiene main chain), TE-2000 (Nippon Soda Co., Ltd., polybutadiene main chain), UC-102M (Kuraray Co., Ltd., isoprene main chain), UC-203M (Kuraray Co., Ltd., isoprene main chain), and BAC-45 (Osaka Organic Chemical Industry Co., Ltd., polybutadiene main chain).

[0019] [1.2. Properties of Component A] Component A is hydrophobic. It is believed that the hydrophobicity of component A improves the moisture barrier properties of the cured product. "Component A is hydrophobic" means that the main chain of component A substantially does not contain hydrophilic groups. If the total number of units in the main chain is taken as 100%, the number of hydrophilic groups contained in the main chain of the hydrophobic polymer may be 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, or 0.1% or less. In one embodiment, the main chain does not contain any hydrophilic groups at all.

[0020] A hydrophilic group is a group that has a highly polar structure. Examples of hydrophilic groups include hydroxyl groups, carboxyl groups, carbonyl groups, ether groups, and amino groups. In one embodiment, a hydrophilic group is a group having one or more atoms selected from the group consisting of oxygen atoms and nitrogen atoms. In one embodiment, a hydrophilic group is a group having heteroatoms other than carbon atoms and hydrogen atoms.

[0021] Component A is preferably a relatively low molecular weight polymer (oligomer). Low molecular weight component A tends to reduce the viscosity of the curable composition. On the other hand, high molecular weight component A tends to reduce shrinkage during curing. Considering these points, the upper limit of the number average molecular weight (Mn) of component A is preferably 60,000 or less, more preferably 40,000 or less, and even more preferably 20,000 or less. The lower limit of the number average molecular weight (Mn) of component A may be, for example, 1,000 or more or 5,000 or more. The average molecular weight is determined on a standard styrene basis by gel permeation chromatography.

[0022] Since component A has a polymerizable (meth)acryloyl group, a cured product can be produced by curing only component A. The lower limit of the glass transition temperature (Tg) of the cured product obtained by curing only component A is preferably -80°C or higher, and more preferably -60°C or higher. The upper limit of the glass transition temperature (Tg) of the cured product obtained by curing only component A is preferably 0°C or lower, and more preferably -10°C or lower. If the glass transition temperature is within the above range, flexibility can be imparted to the resulting cured product. The glass transition temperature can be determined by differential scanning calorimetry (DSC).

[0023] [2. Component B: A monomer that is hydrophobic and has one (meth)acryloyl group] Component B is a monomer that is hydrophobic and has one (meth)acryloyl group. Component B, together with components A and C, forms a crosslinking network triggered by irradiation with active energy rays, thereby curing the curable composition. Component B may consist of only one type of monomer or may contain two or more types of monomers.

[0024] [2.1. Structure of Component B] In one embodiment, component B is represented by the following formula (2), namely, a (meth)acryloyl group and a residue bonded together. In the formula, the structure of the residue is a hydrogen atom or a hydrocarbon group. Examples of hydrocarbon groups include alkyl groups and aryl groups. The structure of the (meth)acryloyl group is as described in Section [1.1]. Equation (2) (residual part) - ((meth)acryloyl group)

[0025] Examples of the residual structure in formula (2) include alkyl groups, cycloalkyl groups, and aryl groups. Examples of component B in which the residual is an alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and behenyl (meth)acrylate. Examples of component B in which the residual part is a cycloalkyl group include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclononyl (meth)acrylate, cyclodecyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanedimethanol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate. An example of component B in which the residual part is an aryl group is benzyl (meth)acrylate.

[0026] Among those mentioned above, one or more selected from the group consisting of isobonyl (meth)acrylate, stearyl (meth)acrylate, and n-octyl (meth)acrylate is preferred, one or more selected from the group consisting of isobonyl acrylate, stearyl acrylate, and n-octyl acrylate is more preferred, and one or more selected from the group consisting of isobonyl acrylate and stearyl acrylate is even more preferred. In particular, when isobonyl acrylate and / or stearyl acrylate are used as component B, excellent moisture barrier properties are achieved, transparency and shrinkage during curing can be reduced.

[0027] [2.2. Properties of Component B] Component B is hydrophobic. Since the polarity of hydrophobic component B is similar to that of component A, it is expected to improve the transparency of the cured product. Furthermore, the hydrophobic nature of component B is also expected to contribute to improved moisture barrier properties of the cured product. "Component B being hydrophobic" means that the remaining portion of component B does not contain hydrophilic groups. An explanation of hydrophilic groups is given in Section [1.2].

[0028] Component B is a monomer. Generally, the molecular weight of component B is smaller than that of the polymer. The molecular weight of component B can be, for example, 600 or less or 400 or less.

[0029] When component B is formed into a homopolymer, the glass transition temperature (Tg) is preferably 0°C or higher, more preferably 20°C or higher, and even more preferably 40°C or higher. Incorporating such a component B tends to reduce the tackiness of the cured product. The glass transition temperature tends to be higher as the rotational degrees of freedom within the homopolymer decrease. Therefore, if the remaining portion of component B has a rigid structure, the glass transition temperature of the homopolymer tends to improve.

[0030] Examples of component B, which has a glass transition temperature of 0°C or higher when homopolymerized, include cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, t-butylcyclohexyl acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.

[0031] [3. Component C: A monomer that is hydrophobic and has two (meth)acryloyl groups] Component C is a monomer that is hydrophobic and has two (meth)acryloyl groups. Component C, together with components A and B, forms a crosslinking network triggered by irradiation with active energy rays, thereby curing the curable composition. Component C may consist of only one type of monomer or may contain two or more types of monomers.

[0032] [3.1. Structure of Component C] In one embodiment, component C is represented by the following formula (3), namely, two (meth)acryloyl groups bonded to an intermediate portion. In the formula, the structure of the intermediate portion is a hydrocarbon group. Examples of hydrocarbon groups include alkylene groups, cycloalkylene groups, and arylene groups. The structure of the (meth)acryloyl group is as described in Section [1.1]. Formula (3) ((meth)acryloyl group)-(intermediate portion)-((meth)acryloyl group)

[0033] Specific examples of component C represented by formula (3) include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, isononanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, Isobornil Examples include di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and 3-methyl-1,5-pentanediol di(meth)acrylate.

[0034] Of the above, tricyclodecanedimethanol di(meth)acrylate is preferred, and tricyclodecanedimethanol diacrylate is more preferred.

[0035] [3.2. Properties of Component C] Component C is hydrophobic. Since the polarity of hydrophobic component C is similar to that of component A, it is thought that the transparency of the cured product will improve. Furthermore, the hydrophobicity of component C is also thought to contribute to improving the moisture barrier properties of the cured product. "Component C is hydrophobic" means that no hydrophilic groups are present in the intermediate portion of component C. An explanation of hydrophilic groups is given in Section [1.2].

[0036] Component C is a monomer. Generally, the molecular weight of component C is smaller than that of the polymer. The molecular weight of component C can be, for example, 600 or less or 400 or less.

[0037] When component C is formed into a homopolymer, the glass transition temperature (Tg) is preferably 0°C or higher, more preferably 50°C or higher, and even more preferably 100°C or higher. When such a component C is incorporated, the tackiness of the cured product tends to be reduced. The glass transition temperature tends to be higher when the rotational degree of freedom within the homopolymer is small. Therefore, if the intermediate portion of component C has a rigid structure, the glass transition temperature of the homopolymer tends to improve.

[0038] Examples of component C whose glass transition temperature is 0°C or higher when homopolymerized include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, isononanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, Isobornil Examples include di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and 3-methyl-1,5-pentanediol di(meth)acrylate.

[0039] [4. Component D: Photoradical polymerization initiator] Component D is a photoradical polymerization initiator (hereinafter sometimes simply referred to as "initiator"). The photoradical polymerization initiator generates radicals upon irradiation with active energy rays (ultraviolet light, visible light, etc.). The generated radicals trigger a crosslinking reaction between (meth)acryloyl groups, causing the curable composition to harden. Component D may consist of only one type of initiator or may contain two or more types of initiators.

[0040] Examples of component D include aromatic ketone initiators (such as α-hydroxyketone initiators and α-aminoketone initiators), acylphosphine oxide initiators, and oxime ester initiators. Of these, α-hydroxyketone initiators are preferred. Using α-hydroxyketone initiators eliminates coloration caused by the initiator and maintains the transparency of the cured product. Furthermore, because of its good curability, tack tends to be reduced.

[0041] Examples of α-hydroxyketone initiators include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Of these, 1-hydroxycyclohexyl phenyl ketone is more preferred.

[0042] [5. Component E: Leveling agent] Component E is a leveling agent. The leveling agent can be any substance that has the function of smoothing the surface of the cured product, and it does not need to be sold as a leveling agent. Leveling agents are also called surface modifiers or smoothing agents. Component E may consist of only one type of leveling agent, or it may contain two or more types of leveling agents. Furthermore, since component E is an optional component, it does not have to be included in the curable composition.

[0043] Examples of component E include acrylic leveling agents, silicone leveling agents, fluorine leveling agents, modified polyether leveling agents, and surface-active polymer leveling agents. Among these, one or more selected from the group consisting of acrylic leveling agents and silicone leveling agents are preferred because they yield highly transparent cured products. Examples of acrylic leveling agents include acrylate polymers and acrylate copolymers. Examples of silicone leveling agents include polydimethylsiloxane, modified polydimethylsiloxane, silicone, and modified silicone.

[0044] [6. Additional ingredients] The curable composition may contain additional components other than those described above (components A to E). Specific examples of such additional components and their preferred content are well known to those skilled in the art. Examples of additional components include photosensitizers, wetting agents, adhesion promoters, fillers, thixotropic agents, silane coupling agents, solvents, colorants, stabilizers, defoamers, and slip agents.

[0045] [7. Composition of the curable composition] In the curable composition, the content of component A is greater than the combined content of components B and C. It is believed that this compositional ratio improves the adhesive properties of the curable composition. In one embodiment, the value of "content of component A - (content of component B + content of component C)" is greater than 0 and less than or equal to 50.

[0046] In the curable composition, the lower limit of the "content of component B / content of component C" is 0.5 or higher, preferably 0.7 or higher, and more preferably 1.0 or higher. In the curable composition, the upper limit of the "content of component B / content of component C" is 4.0 or lower, preferably 3.0 or lower, and more preferably 2.5 or lower. It is believed that the adhesive properties of the curable composition will be improved by adopting such compositional ratios.

[0047] Assuming the total weight of the curable composition is 100% by weight, the lower limit of the content of component A is preferably 40% by weight or more, and more preferably 45% by weight or more. The upper limit of the content of component A is preferably 70% by weight or less, and more preferably 60% by weight or less.

[0048] Assuming the total weight of the curable composition is 100% by weight, the lower limit of the content of component B is preferably 10% by weight or more, and more preferably 20% by weight or more. The upper limit of the content of component B is preferably 40% by weight or less, and more preferably 30% by weight or less. However, the content of component B is less than the content of component A.

[0049] Assuming the total weight of the curable composition is 100% by weight, the lower limit of the content of component C is preferably 10% by weight or more, and more preferably 11% by weight or more. The upper limit of the content of component C is preferably 20% by weight or less, and more preferably 15% by weight or less.

[0050] Assuming the total weight of the curable composition is 100% by weight, the lower limit of the content of component D is preferably 0.3% by weight or more, and more preferably 1% by weight or more. The upper limit of the content of component D is preferably 10% by weight or less, and more preferably 8% by weight or less.

[0051] Assuming the total weight of the curable composition is 100% by weight, the lower limit of the content of component E is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more. The upper limit of the content of component E is preferably 3% by weight or less, and more preferably 1% by weight or less.

[0052] [8. Cured products and their uses] A cured product according to one aspect of the present invention is obtained by curing the above-described curable composition. When the curable composition is irradiated with active energy rays (ultraviolet light, visible light, etc.), a crosslinking reaction proceeds between (meth)acryloyl groups, and a cured product is obtained.

[0053] The cured product exhibits high moisture barrier properties and transparency, and reduces tack and shrinkage associated with curing, making it suitable for use as a component (such as a encapsulant) in semiconductor devices (especially organic semiconductor devices). Examples of semiconductor devices include LEDs, OLEDs (organic light-emitting diodes), and QLEDs. More specific examples include flexible OLEDs, transparent OLEDs, flexible and transparent OLEDs, mini-LEDs, micro-LEDs, and micro-OLEDs.

[0054] Regarding moisture barrier properties, the water vapor transmission rate (WVTR) of the cured product is 80 g / m². 2 Less than 40 g / m² is preferable. 2 Less than 1 day is preferable. The specific method for measuring WVTR is as described in the examples.

[0055] Regarding transparency, the haze of the cured product with a thickness of 100 μm is preferably less than 0.8%, and more preferably less than 0.5%. The method for measuring the haze is as described in the examples.

[0056] Regarding shrinkage during curing, the amount of warping of the glass plate when a curable composition applied to a predetermined area of ​​the glass plate is cured is preferably less than 10 mm, and more preferably less than 5 mm. The method for measuring the amount of warping is as described in the examples.

[0057] Regarding adhesion, the fracture stress when the cured material was subjected to a tensile test was 100 N / cm². 2 The above is preferable, with a pressure of 300 N / cm². 2 The above is more preferable. The method for the tensile test is as described in the examples.

[0058] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are included within the technical scope of the present invention. [Examples]

[0059] 〔material〕 The materials used in the examples and comparative examples are as follows: ●Ingredient A • Polymer 1: CN9014 (Sartomer, hydrogenated polybutadiene main chain, Mw: 23,000, Tg of cured product obtained by curing Polymer 1 alone: ​​-41℃) • Polymer 2: TEAI-1000 (Nippon Soda Co., Ltd., hydrogenated polybutadiene main chain, Mn: 2,000, Tg: -14℃ of cured product obtained by curing only Polymer 2) • Polymer 3: TE-2000 (Nippon Soda Co., Ltd., polybutadiene main chain, Mn: 2,500) • Polymer 4: UC-102M (Kuraray Co., Ltd., isoprene main chain, Mn: 17,000, Tg: -60℃ of cured product obtained by curing only Polymer 4) ● Polymers other than component A • Polymer 5: ARUFON UP-1110 (Toagosei Co., Ltd., acrylic main chain (without (meth)acryloyl groups), Mw: 2,500, Tg of homopolymer: -64℃) ●Ingredient B • 1-functional monomer 1: IBOA-B (Daicel Ornex Corporation, isobornyl acrylate, Tg of homopolymer: 97℃) • 1-functional monomer 2: Light acrylate SA (Kyoeisha Chemical Co., Ltd., stearyl acrylate, Tg of homopolymer: 30℃) • 1-functional monomer 3: NOAA (Osaka Organic Chemical Industry Co., Ltd., n-octyl acrylate, Tg of homopolymer: -65℃) ● Monofunctional monomers other than component B • 1-Functional Monomer 4: ACMO (KJ Chemicals Co., Ltd., Acryloyl Morpholine (High Polarity Monomer)) ●Component C • Bifunctional monomer 1: A-DCP (Shin-Nakamura Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate, Tg of homopolymer: 186℃) ●Component D • Photoradical polymerization initiator 1: Omnirad184 (IGM RESINS, 1-hydroxycyclohexyl-phenyl ketone (α-hydroxyketone type initiator)) ● Component E · Levelling agent 1: UVX-35 (Namboku Chemical Co., Ltd., acrylic copolymer) · Levelling agent 2: L-1983N (Namboku Chemical Co., Ltd., acrylic copolymer) · Levelling agent 3: BYK-UV3500 (BYK, acrylic group-containing modified polydimethylsilicone)

[0060] 〔Evaluation method〕 The properties of the cured products obtained from the curable compositions according to the examples and comparative examples were evaluated as follows.

[0061] (1) Moisture barrier property The water vapor transmission rate (WVTR) of the sample was measured by the cup method to evaluate the moisture barrier property. The smaller the WVTR, the higher the moisture barrier property. The specific measurement procedure is as follows. 1. The curable composition was spread on a release sheet and irradiated with 1 J of ultraviolet light. A metal halide lamp (Takeiden Co., Ltd.) was used for the ultraviolet light irradiation (the same applies hereinafter). In this way, a sheet-like cured product with a thickness of 100 μm and a diameter of 7 cm was obtained. 2. 7 g of calcium chloride (Kishida Chemical Co., Ltd.) was placed in an aluminum cup. A sheet-like cured product and an O-ring were stacked on the opening of the cup, and the periphery was sealed with molten paraffin. The permeation part of the sheet-like cured product was a circle with a diameter of 6 cm. 3. It was allowed to stand for 24 hours under the conditions of a temperature of 40°C and a relative humidity of 90%. 4. Based on the increase in weight, the WVTR of the sample was calculated by the following formula. WVTR (g / m 2 ·day) = increased weight (g) ÷ {0.03 × 0.03 × 3.14 (m 2 ) × 1 (day)}

[0062] [Evaluation criteria] · ++: WVTR is less than 40 g / m 2 ·day · +: WVTR is 40 g / m or more and less than 80 g / m 2 ·day 2 ·day ·- :WVTR is 80g / m 2 • days or more

[0063] (2) Transparency The haze of the sample was measured to evaluate its transparency. A smaller haze indicates higher transparency. The specific measurement procedure is as follows: 1. The curable composition was dropped onto a glass slide. Another glass slide was then placed on top, and the two slides were bonded together so that the thickness of the curable composition was 100 μm. 2. The curable composition was cured by irradiating it with 1 joule of ultraviolet light. 3. The haze of the sample was measured according to JIS K 7361-1. The measurement was performed at room temperature (25°C). A haze meter (HAZE METER NDH-5000, Nippon Denshoku Industries Co., Ltd.) was used for the measurement.

[0064] [Evaluation Criteria] ·++: Haze is less than 0.5% • + : Haze is 0.5% or more, but less than 0.8% ·- : Haze is 0.8% or higher

[0065] (3) Reduction of tack A trained sensory panel evaluated the tack of the samples. Specifically, (4) the tack was evaluated by lightly touching the surface of the cured material prepared by shrinkage during curing with a finger.

[0066] [Evaluation Criteria] •++: The hardened material does not stick to your fingers. •+: The hardened material sticks to your finger but comes off easily. - : The hardened material sticks to my finger and won't come off.

[0067] (4) Shrinkage due to hardening The amount of warpage of the sample was measured, and the shrinkage during curing of the curable composition was evaluated. A smaller amount of warpage indicates less shrinkage during curing. The specific measurement procedure is as follows. 1. 1.0 g of the curable composition was smoothly applied to one side of a glass plate (150 mm × 10 mm × 0.4 mm). The dimensions of the applied area were width: 10 mm × length: 120 mm. 2. The curable composition was cured by irradiating it with 1 joule of ultraviolet light. 3. Allow to cool at room temperature (25°C) for 1 hour. 4. The amount of glass warping (mm) was measured with a ruler.

[0068] [Evaluation Criteria] •++: Curvature less than 5mm •+ : Curvature of 5mm or more, less than 10mm ·- : Curvature of 10mm or more

[0069] (5) Smoothness during application In step 1 of the sample warpage measurement, the surface shape of the applied curable composition was visually confirmed.

[0070] [Evaluation Criteria] •++: Smooth within 1 minute after application. •+: Smooth within 10 minutes after application.

[0071] (6) Adhesive strength The tensile shear adhesive strength of samples bonded with a curable composition was measured to evaluate the adhesive strength. Higher tensile shear adhesive strength indicates better adhesion. The specific measurement procedure is as follows. 1. A curable composition was applied between two glass microscope slides (1 cm in diameter, 20 μm thick) and cured by ultraviolet irradiation. 2. A tensile shear test was performed at room temperature. An Autograph (AGS-H 500N, Shimadzu Corporation) was used for the tensile shear test. The tensile speed was set to 5 mm / min, and the adhesive strength was evaluated by measuring the breaking force.

[0072] [Evaluation Criteria] •++: Adhesive strength of 300 N / cm 2 That's all. •+: Adhesion strength of 100 N / cm 2More than 300N / cm 2 less than - : Adhesive strength of 100 N / cm 2 less than

[0073] [Examples 1-10, Comparative Examples 1-8] Each material was weighed out in the quantities listed in Table 1. These materials were stirred using a rotary-orbit mixer or stirrer until no undissolved particles remained. In this way, a curable composition was obtained.

[0074] [Table 1] JPEG0007882674000002.jpg194140

[0075] 〔result〕 In Example 3, component A was reduced and components B and C were increased compared to Example 1. In Example 4, unlike Example 1, component E was not included. In Examples 5-7, a different component A was included than in Example 1. In Examples 8-9, a different component B was included than in Example 1. In Example 10, a different component E was included than in Example 1. Curable compositions according to all examples yielded cured products with excellent moisture barrier properties and transparency, and reduced tack and shrinkage associated with curing.

[0076] In Comparative Example 1, when component A was not included, shrinkage during curing was significant. In Comparative Example 2, when component B was not included, shrinkage during curing was significant. In Comparative Example 3, when component C was not included, the tack of the cured product was significant. In Comparative Example 4, when component C was included in excess, shrinkage during curing was significant. In Comparative Example 5, when component A was included in insufficient amounts and component B was included in excess, and the content of component B was greater than that of component A, the tack of the cured product was significant. In Comparative Example 6, when a hydrophilic acrylic polymer without a (meth)acryloyl group was included instead of component A, the moisture barrier properties decreased and the tack of the cured product also increased. In Comparative Example 7, when a highly polar monofunctional monomer was included instead of component B, the transparency of the cured product decreased and the smoothness of the curable composition also deteriorated.

[0077] Comparing Example 2 and Example 9, it can be seen that incorporating component B, which has a high glass transition temperature (above 0°C) when used as a homopolymer, is preferable from the viewpoint of superior moisture barrier properties, reduced tack of the cured product, and improved adhesive strength. Comparing Examples 2, 5-6 and Example 7, it can be seen that having polybutadiene or hydrogenated polybutadiene as the main chain skeleton of component A is preferable from the viewpoint of moisture barrier properties and adhesive strength. [Industrial applicability]

[0078] This invention can be used in semiconductor devices and the like.

Claims

1. A curable composition for semiconductor devices containing the following components A to D, Component A: A hydrophobic polymer having (meth)acryloyl groups. Component B: A monomer that is hydrophobic and has one (meth)acryloyl group. Component C: A monomer that is hydrophobic and has two (meth)acryloyl groups. Component D: Photoradical polymerization initiator The amount of component A is greater than the total amount of component B and component C. The ratio of the content of component B to the content of component C is between 0.5 and 4.

0. The glass transition temperature of the monomer B described above, when it is a homopolymer, is 0°C or higher. The (meth)acryloyl group of component A is bonded to the main chain via a spacer. At least one of the above spacer and the bonding portion between the above spacer and the (meth)acryloyl group has a urethane bond. The above component C is one or more selected from the group consisting of 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, isononanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, isobornyl di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and 3-methyl-1,5-pentanediol di(meth)acrylate. If the total weight of the above-mentioned curable composition for semiconductor devices is 100% by weight, The content of component A is 40 to 70% by weight. The content of component B is 10 to 40% by weight. The content of component C is 10 to 20% by weight. Curable composition for semiconductor devices.

2. A curable composition for semiconductor devices containing the following components A to D, Component A: A hydrophobic polymer having (meth)acryloyl groups. Component B: A monomer that is hydrophobic and has one (meth)acryloyl group. Component C: A monomer that is hydrophobic and has two (meth)acryloyl groups. Component D: Photoradical polymerization initiator The amount of component A is greater than the total amount of component B and component C. The ratio of the content of component B to the content of component C is between 0.5 and 2.

1. The glass transition temperature of the monomer B described above, when it is a homopolymer, is 0°C or higher. The (meth)acryloyl group of component A is bonded to the main chain via a spacer. At least one of the above spacer and the bonding portion between the above spacer and the (meth)acryloyl group has a urethane bond. If the total weight of the above-mentioned curable composition for semiconductor devices is 100% by weight, The content of component A is 40 to 70% by weight. The content of component B is 10 to 40% by weight. The content of component C is 10 to 20% by weight. Curable composition for semiconductor devices.

3. The curable composition for semiconductor devices according to claim 1, wherein the ratio of the content of component B to the content of component C is 0.5 to 2.

1.

4. The curable composition for semiconductor devices according to any one of claims 1 to 3, wherein the main chain of component A is polybutadiene or hydrogenated polybutadiene.

5. The curable composition for semiconductor devices according to any one of claims 1 to 4, wherein the glass transition temperature when the monomer C is a homopolymer is 0°C or higher.

6. It also contains the following ingredient E: Component E: Leveling agent The curable composition for semiconductor devices according to any one of claims 1 to 5, wherein the above component E is one or more selected from the group consisting of acrylic leveling agents and silicone leveling agents.

7. The curable composition for semiconductor devices according to any one of claims 1 to 6, wherein component D is an α-hydroxyketone type photoradical polymerization initiator.

8. A curable composition for semiconductor devices according to any one of claims 1 to 7, wherein, other than component B, it does not contain a monomer having a hydrophilic group and one (meth)acryloyl group.

9. A cured semiconductor device product obtained by curing a curable composition for semiconductor devices according to any one of claims 1 to 8.

10. A semiconductor device comprising a cured product for semiconductor devices as described in claim 9.