JP6223133B2 - Thermosetting resin composition - Google Patents

Description

The present invention relates to a thermosetting resin composition.

In recent years, an optical semiconductor device is used as a light source of a light emitting display device or a lighting device. In an optical semiconductor device, a light emitting element is mounted on a resin package including a lead frame and a resin molded body, and after wiring with a wire or the like, the light emitting element is covered with a sealing resin. The resin molded body used for this resin package serves as a reflector for reflecting light and a container for filling a sealing resin. The resin package is obtained by transfer molding a thermosetting resin composition molded into a tablet mold onto a lead frame.

When the thermosetting resin composition is transfer molded to the lead frame, the resin package is warped due to the difference in coefficient of linear expansion between the lead frame and the resin molded body because of heating and cooling. This makes it difficult to proceed with subsequent steps.

In patent document 1, in order to reduce the curvature of a resin package, compounding a filler with the thermosetting resin composition which forms a resin molding is disclosed. That is, it is disclosed that by blending a filler, the linear expansion coefficient of the thermosetting resin composition can be controlled, the difference in the linear expansion coefficient from the lead frame can be reduced, and warpage can be reduced. ing.

JP 2011-035082 A

However, the method of blending a filler with a thermosetting resin composition has a problem that the blending amount of the filler is limited in order to maintain tablet manufacturability, and it is filled to reduce the linear expansion coefficient. When the amount of the material was increased, there was a problem that gate clogging occurred during transfer molding.

Then, this invention makes it a subject to provide the thermosetting resin composition which can adjust the curvature of a resin package easily.

In order to solve the above problems, the thermosetting resin composition of the present invention comprises a compound represented by the following general formula (1) and a glycidyl (meth) acrylate polymer. The warpage of the resin package can be improved by combining the thermosetting compound represented by the following general formula (1) and the glycidyl (meth) acrylate polymer, and further, depending on the amount of addition of the glycidyl (meth) acrylate polymer. It becomes possible to adjust the linear expansion coefficient.

(In said general formula (1), X < ¹ >, X < ² > and X < ³ > show the substituent represented by the following general formula (A) or (B) each independently, X < ¹ >, X < ² > and X < ³ > (At least one of them is a substituent represented by the following general formula (A).)
(In the above general formulas (A) and (B), Y ^{1 to} Y ⁴ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C 1-10 linear aliphatic hydrocarbon group, substituted or Any of a linear aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group M is an integer of 1 to 10 and n is an integer of 0 to 3. When n is 0, R is a hydrogen atom, a substituted or unsubstituted linear fatty acid having 1 to 20 carbon atoms. Aromatic hydrocarbon group, substituted or unsubstituted C3-C10 branched aliphatic hydrocarbon group, substituted or unsubstituted C3-C10 alicyclic aliphatic hydrocarbon group, or substituted or unsubstituted Any one of aromatic hydrocarbon groups, when n is 1 to 3, R is a single bond, Or an unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon group having 3 to 10 carbon atoms. It represents either an alicyclic aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group, and Z represents a substituent represented by the following general formula (C).
(In the general formula (C), X ⁴ and X ⁵ represent a substituent represented by the general formula (B). In the general formula (C), Y ^{1 to} Y ⁴ are each independently a hydrogen atom. , Halogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted linear aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number It represents any of 3 to 10 alicyclic aliphatic hydrocarbon groups or substituted or unsubstituted aromatic hydrocarbon groups, m is an integer of 1 to 10, and n is an integer of 0 to 3. Is 0, R is a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, A substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms or a substituted or unsubstituted Any one of aromatic hydrocarbon groups, when n is 1 to 3, R is a single bond, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon A branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group)

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the thermosetting resin composition which can adjust the curvature of a resin package.

It is a figure which shows the example of the lead frame used in an Example.

The thermosetting composition of this invention is characterized by including the compound shown by the said General formula (1).

Examples of the halogen represented by Y ¹ , Y ² , Y ^3, and Y ^{4 in the} general formulas (A), (B), and (C) include F, Cl, Br, and I.

In addition, examples of the linear aliphatic hydrocarbon group represented by Y ¹ , Y ² , Y ^3, and Y ^{4 in the} general formulas (A), (B), and (C) include a methyl group, an ethyl group, and n- A propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned.

Examples of the branched aliphatic hydrocarbon group represented by Y ¹ , Y ² , Y ^3, and Y ^{4 in the} general formulas (A), (B), and (C) include isopropyl group, isobutyl group, s- Butyl group, t-butyl group, isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, isohexyl group, s-hexyl group , T-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group Group, cycloheptyl group, n-octyl group, isooctyl group, s-octyl group, t-octyl group, neooctyl group, 2-ethylhexyl group, isononyl group, s-nonyl group, - nonyl group, neononyl group, isodecyl group, s- decyl, t-decyl group, and the like neodecyl group

In addition, examples of the alicyclic aliphatic hydrocarbon group represented by Y ¹ , Y ² , Y ^3, and Y ^{4 in the} general formulas (A), (B), and (C) include, for example, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Group, cyclohexyl group, decalyl group, norbornyl group, adamantyl group and the like.

In addition, examples of the aromatic hydrocarbon group represented by Y ¹ , Y ² , Y ^3, and Y ^{4 in the} general formulas (A), (B), and (C) include a phenyl group, a naphthyl group, and an anthracyl group. It is done.

Also, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, alicyclic rings represented by Y ¹ , Y ² , Y ³ and Y ^{4 in the} general formulas (A), (B) and (C). Examples of the substituent for the aliphatic hydrocarbon group and aromatic hydrocarbon group include halogen such as F, Cl, Br, and I, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number Examples thereof include 1 to 10 alkylthio groups.

In the general formulas (A), (B), and (C), Y ¹ , Y ² , Y ^3, and Y ⁴ are preferably hydrogen atoms. In this case, in the general formulas (A), (B), and (C), the compound represented by the general formula (1) as compared with the case where Y ¹ , Y ² , Y ^3, and Y ⁴ are other than a hydrogen atom. Can be handled easily.

  In the general formulas (A), (B), and (C), m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and particularly preferably 1. In particular, when m is 1, since the raw material can be easily obtained and the reactivity is high, there is an advantage that a cured product can be obtained in a short curing time.

  Moreover, as mentioned above, in the said general formula (A), n is an integer of 0-3. In this case, since it becomes a thermosetting compound with a low viscosity, the advantage that it can handle easily on an operation | work is acquired.

  Examples of the linear aliphatic hydrocarbon group represented by R in the general formula (A) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n- Heptyl, n-octyl, n-nonyl, n-decyl, methyl, ethyl, propyl, n-butyl, n-hexyl, methylene, ethylene, propylene, n-butylene, Examples thereof include n-hexylene group.

  Examples of the branched aliphatic hydrocarbon group represented by R in the general formula (A) include isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, s-pentyl group, t- Pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2 -Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group, cycloheptyl group, n-octyl group, isooctyl group, s-octyl group T-octyl group, neooctyl group, 2-ethylhexyl group, isononyl group, s-nonyl group, t-nonyl group, neononyl group, isodecyl group, s Decyl, t-decyl group, etc. neodecyl group.

  Examples of the alicyclic aliphatic hydrocarbon group represented by R in the general formula (A) include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, decalinyl group, norbornyl group, adamantyl group, and cyclopropylene. Group, cyclobutylene group, cyclopentylene group, cyclohexylene group, decalinylene group, norbornylene group, adamantylene group and the like.

  Examples of the aromatic hydrocarbon group represented by R in the general formula (A) include a phenyl group, a naphthyl group, an anthracyl group, a phenylene group, a naphthylene group, and an anthracylene group.

  In addition, even if the linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, alicyclic aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R in the general formula (A) have Examples of suitable substituents include halogens such as F, Cl, Br, and I, hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkylthio groups having 1 to 10 carbon atoms. .

  In the general formula (A), R preferably represents a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms. In this case, there exists an advantage that the thermostability of a thermosetting compound and the hardened | cured material obtained using this is high.

The thermosetting composition of the present invention includes a glycidyl (meth) acrylate polymer. The glycidyl acrylate polymer is preferably a homopolymer of glycidyl (meth) acrylate or a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer. In this case, the glycidyl (meth) acrylate polymer is easily available, and has an advantage of high compatibility with the epoxy resin.

In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid.

Specific examples of the (meth) acrylate glycidyl polymer include the following (meth) acrylate glycidyl polymers. Marproof G-0110 (weight average molecular weight 12,000, epoxy equivalent 170 g / eq., Manufactured by NOF Corporation), Marproof G-0150M (weight average molecular weight 8,000-10,000, epoxy equivalent 310 g / eq., NOF Corporation), Marproof G-2050M (weight average molecular weight 200,000-250,000, epoxy equivalent 340 g / eq., Manufactured by NOF Corporation), Marproof G-017581 (weight average molecular weight 10,000, epoxy) Equivalent 240 g / q., Manufactured by NOF Corporation), Marproof G-0250SP (molecular weight 2,000, epoxy equivalent 310 g / eq., Manufactured by NOF Corporation), and the like.

The content of the (meth) acrylic acid glycidyl polymer is preferably 0.01 to 30% by mass with respect to the thermosetting compound. When the content of the (meth) acrylate glycidyl polymer is less than 0.01% by mass, the warpage of the resin package cannot be adjusted sufficiently, and when it exceeds 30% by mass, the time required for curing becomes long. It may affect the curability.

The thermosetting composition of the present invention may further include a curing agent, a curing accelerator, and an inorganic filler.

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

(Synthesis Example 1)
480 g (1.6 mol) of triglycidyl cyanurate (manufactured by Nippon Carbide Industries Co., Ltd.) was put into a 1 L beaker, and triglycidyl cyanurate was heated while heating the beaker in an oil bath adjusted so that the internal temperature of the beaker became 70 ° C. Stir and melt. Subsequently, 20 g (0.12 mol) of 1,4-cyclohexanedicarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was charged into the beaker over 1 hour 30 minutes. Then, it heated with stirring for 30 minutes in the state which maintained the temperature of the content of a beaker at 70 degreeC, and obtained the composition. The composition was separated and purified by silica gel column chromatography to obtain a compound. The NMR of the compound is shown below.

¹ H-NMR (CDCl ₃ , 400 MHz): σ
ppm 4.665 (dd, J = 3.2, 12.0 Hz, 4H), 4.350-4.305 (m, 4H), 4.232 (m, 2H), 3.967 (dd, J = 1.2, 12.8 Hz, 2H), 3.613 (dd, J = 4.0, 12.8 Hz, 2H), 3.373 (m, 4H), 3.160 (m, 2H), 2. 897 (m, 4H), 2.815 (m, 2H), 2.748 (m, 4H), 2.309 (m, 2H), 1.903-1.228 (m, 8H)

(Examples 1-4, Comparative Example 1)
The composition obtained in Synthesis Example 1, the glycidyl (meth) acrylate polymer, and the inorganic filler are blended so as to have the composition shown in Table 1, and roll kneading is performed at 50 to 60 ° C. for 10 minutes, and thermosetting is performed. A functional resin composition was obtained.

(Lead frame)
A circuit including a lead electrode was produced by using a general etching on a 50 mm × 50 mm × 0.15 mm copper frame, and then this circuit was subjected to Ag plating to obtain a lead frame. FIG. 1 shows an example of a lead frame.
(Sample preparation)
The thermosetting resin composition was molded to produce a tablet. The tablet and the lead frame were heated at a mold temperature of 180 ° C., a pressure of 0.16 MPa, and a curing time of 2 minutes. .
(Warp evaluation)
In the warpage evaluation, the convex surface of the test piece was placed on a smooth plate, one corner of the test piece was held with a finger, and the height from the other flat smooth plate on the diagonal was measured with a ruler. .
(Measurement of linear expansion coefficient)
Each thermosetting composition was heated and pressure-molded at a mold temperature of 180 ° C., a pressure of 0.16 MPa, and a curing time of 2 minutes, followed by post-treatment at 150 ° C. for 2 hours, and a test of 20 mm × 2 mm × 1 mm. A piece was made. Next, TMA4000SA manufactured by Burker AXS was used to measure from 30 ° C. to 250 ° C. at a rate of 50 ° C./min, and the dimensional change amount of each test piece was obtained. The linear expansion coefficient was determined from the values obtained from 50 ° C. to 170 ° C.

“-” In the table indicates that it is not blended.
<Glycidyl acrylate polymer>
: Marproof G-0150M (molecular weight 8,000-10,000, epoxy equivalent 310 g / eq., Manufactured by NOF Corporation)
: Marproof G-0110 (molecular weight 12,000, epoxy equivalent 170 g / eq., Manufactured by NOF Corporation)
<Inorganic filler>
: Silica (FB-304, average particle size 6 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.)
: Titanium oxide (CR-90-2, average particle size 0.3 μm, manufactured by Ishihara Sangyo Co., Ltd.)

From the results shown in Table 1, when the thermosetting composition of the present invention to which a glycidyl (meth) acrylate polymer is added is used for a resin package, the warpage of the resin package is reduced. Was confirmed. Moreover, it was confirmed that the linear expansion coefficient can be adjusted by the addition amount of the glycidyl (meth) acrylate polymer.

By using the thermosetting composition of the present invention, it is possible to reduce or adjust the warp that appears during the production of a semiconductor element package, and therefore it can be suitably used for a semiconductor package.

1 ... Lead frame

Claims (5)

A thermosetting resin composition comprising a compound represented by the following general formula (1) and a glycidyl (meth) acrylate polymer.
(In said general formula (1), X < ¹ >, X < ² > and X < ³ > show the substituent represented by the following general formula (A) or (B) each independently, X < ¹ >, X < ² > and X < ³ > (At least one of them is a substituent represented by the following general formula (A).)
(In the above general formulas (A) and (B), Y ^{1 to} Y ⁴ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C 1-10 linear aliphatic hydrocarbon group, substituted or Any of a linear aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group M is an integer of 1 to 10 and n is an integer of 0 to 3. When n is 0, R is a hydrogen atom, a substituted or unsubstituted linear fatty acid having 1 to 20 carbon atoms. Aromatic hydrocarbon group, substituted or unsubstituted C3-C10 branched aliphatic hydrocarbon group, substituted or unsubstituted C3-C10 alicyclic aliphatic hydrocarbon group, or substituted or unsubstituted Any one of aromatic hydrocarbon groups, when n is 1 to 3, R is a single bond, A substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 to 10 Or an alicyclic aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group, and Z represents a substituent represented by the following general formula (C).
(In the general formula (C), X ⁴ and X ⁵ represent a substituent represented by the general formula (B). In the general formula (C), Y ^{1 to} Y ⁴ are each independently a hydrogen atom. , Halogen, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted linear aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number It represents any of 3 to 10 alicyclic aliphatic hydrocarbon groups or substituted or unsubstituted aromatic hydrocarbon groups, m is an integer of 1 to 10.
The glycidyl (meth) acrylate polymer is a homopolymer of glycidyl (meth) acrylate or a copolymer of glycidyl (meth) acrylate and a radically polymerizable monomer. Thermosetting composition. The thermosetting composition according to claim 1 or 2, wherein in the general formulas (A), (B), and (C), Y ¹ , Y ² , Y ^3, and Y ⁴ are hydrogen atoms. The thermosetting composition according to any one of claims 1 to 3, wherein m is 1 in the general formulas (A), (B), and (C). The thermosetting composition according to any one of claims 1 to 4, wherein, in the general formula (A), R is a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms.