阅读说明：本技术 树脂组合物用填料、含填料的浆料组合物以及含填料的树脂组合物 (Resin combination filler, the paste compound containing filler and the resin combination containing filler ) 是由 荻本伸太 富田亘孝 中野修 于 2017-07-28 设计创作，主要内容包括：本发明的要解决的课题在于提供一种树脂组合物用填料,含有该树脂组合物用填料能够降低热膨胀系数。明确了二氧化硅材料中具有由FAU型、FER型、LTA型、MFI型和/或MWW型构成的晶体结构的结晶性二氧化硅质材料具有负的热膨胀系数,但分散在树脂材料中时,会促进该树脂材料的黄变。因此,发现可以通过利用由有机硅化合物构成的表面处理剂对结晶性二氧化硅质材料进行处理,使作为树脂材料黄变的一个原因的来自铝元素的活性点失活,从而能够抑制黄变。而且,即使以能够抑制黄变的程度在表面形成来自表面处理剂的层,也能够将热膨胀系数保持在负的范围。(The project to be solved of the invention is to provide a kind of resin combination filler, can reduce thermal expansion coefficient with filler containing the resin combination.Specify that the crystallinity silica material in earth silicon material with the crystal structure being made of FAU type, FER type, LTA type, MFI type and/or MWW type has negative thermal expansion coefficient, but when being dispersed in resin material, the xanthochromia of the resin material can be promoted.Thus, it is found that the active site inactivation from aluminium element of a reason as resin material xanthochromia can be made, so as to inhibit xanthochromia by handling using the surface treating agent being made of organo-silicon compound crystallinity silica material.Moreover, thermal expansion coefficient can be also maintained to negative range even if forming the layer from surface treating agent to be able to suppress the degree of xanthochromia on surface.)

1. a kind of resin combination filler, contains in resin combination and used, the resin combination is tool with filler There are the filler material of crystallinity siliceous particulate material and surface treating agent, the siliceous particulate material of crystallinity With the crystal structure being made of FAU type, FER type, LTA type, MFI type and/or MWW type, the surface treating agent by with it is described The surface of the siliceous particulate material of crystallinity is reacted or the organo-silicon compound of attachment are constituted,

The amount of the surface treating agent is the range that the filler material shows negative thermal expansion coefficient.

2. resin combination filler according to claim 1, wherein the organo-silicon compound are selected from silazane And/or wantonly a kind or more in silane coupling agent.

3. resin combination filler according to claim 1 or 2, wherein on the basis of all quality, aluminium element Content is 12% or less.

4. resin combination filler described in any one of claim 1 to 3, wherein the crystal structure is FAU Type.

5. resin combination filler according to any one of claims 1 to 4, wherein in the tree for mounting material Contain in oil/fat composition and uses.

6. a kind of paste compound containing filler, have resin combination filler according to any one of claims 1 to 5 and Disperse the solvent of the resin combination filler.

7. a kind of resin combination containing filler, have resin combination filler according to any one of claims 1 to 5 and Disperse the resin material of the resin combination filler.

Technical field

The present invention relates to contain in resin combination and use resin combination filler, containing the resin combination Slurry with filler containing filler and contain the resin combination containing filler of the resin combination filler.

Background technique

In the past, for adjustment thermal expansion coefficient the purpose of, used in the encapsulating materials such as printing distributing board, sealing material Cooperate inorganic particulate as filler in resin combination.It is main wide as filler in order to which thermal expansion coefficient is low, insulating properties is excellent It is general to use amorphous silica particle.

In recent years, with the requirement of the multifunction of electronic equipment, semiconductor packages constantly further slimming, high density Change, influence of the thermal expansion, warpage of semiconductor packages to reliability becomes much larger.Therefore, carrying out reduction printing distributing board, The thermal expansion coefficient of the solidfied material of resin combination used in sealing material and reduce thermal expansion, the research of warpage (patent text Offer 1 etc.).

Summary of the invention

In view of above-mentioned actual conditions, the project to be solved of the invention is to provide one kind by containing in resin combination There is and can reduce the resin combination filler of coefficient of thermal expansion.

In order to solve the above problems, the inventors of the present invention have carried out thermal expansion coefficient is lower than amorphous silica and have heated When the material with negative thermal expansion coefficient that shrinks be applied to the research of filler material.As with negative thermal expansion coefficient Material can be enumerated by beta-eucryptite (LiAlSiO₄), tungsten wire array (ZrW₂O₈) constitute particle (patent document 2,3).But β- Eucryptite contains Li as main composition element, and since the diffusion of Li ion reduces insulating properties, it is insufficient that accordingly, there exist electrical characteristics The problem of.Various researchs have been carried out to tungsten wire array, the time expended has been synthesized and cost is big, although with laboratory-grade manufacture There are many report, but not yet establish the method industrially manufactured.

Then, specifying in silica material has by FAU type, FER type, LTA type, MFI type and/or MWW type The crystallinity silica material of crystal structure has negative thermal expansion coefficient, but when being dispersed in resin material, promoting should The xanthochromia of resin material.

To promoting xanthochromia to be studied, as a result know contained in these crystallinity silica materials from aluminium member The hydroxyl of element becomes active site and acts on resin.Thus, it is found that can be by utilizing the surface being made of organo-silicon compound Inorganic agent handles crystallinity silica material, and can make a reason as resin material xanthochromia comes from aluminium Active site inactivation, so as to inhibit xanthochromia.Even if being formed with being able to suppress the degree of xanthochromia on surface from surface Thermal expansion coefficient can be also maintained at negative range by the layer of inorganic agent.

The present invention is completed based on above-mentioned opinion, and the resin combination filler of the invention for solving the above subject exists Contain in resin combination and use, the resin combination is with the siliceous particulate material of crystallinity and table with filler The filler material of surface treatment agent, the siliceous particulate material of crystallinity have by FAU type, FER type, LTA type, MFI type And/or the crystal structure that MWW type is constituted, the surface treating agent is by the surface with the siliceous particulate material of the crystallinity The organo-silicon compound of reaction or attachment are constituted,

The amount of the surface treating agent is the range that the filler material shows negative thermal expansion coefficient.

Here, as the organo-silicon compound, be preferably selected from wantonly a kind in silazane and/or silane coupling agent with On.If xanthochromia can be effectively inhibited as surface treating agent using them.

In turn, preferably on the basis of all quality, the content of aluminium element is 12% or less.Lead to xanthochromia by reducing The original amount of aluminium element can effectively inhibit xanthochromia.

In addition, the crystallinity silica material of FAU type has high negative expansion coefficient, suitable for inhibiting thermal expansion Purpose.

These resin combination filler systems are preferably contained in the resin combination for the mounting material of electronic component And it uses.If the thermal expansion coefficient of resin combination is big, due to face direction thermal expansion and cause to produce in solder connection Raw crackle, or due to thickness direction thermal expansion and cause to generate poor flow in the interlayer of printing distributing board.In addition, due to The difference of the thermal expansion coefficient of each component is big, is easy to produce the warpage of semiconductor packages.By reducing thermal expansion coefficient, it is able to suppress The generation of these unfavorable conditions.In addition, if there is positive heat with being used only using resin combination filler of the invention The case where previous filler of the coefficient of expansion, is compared, and desired thermal expansion system can be realized with less filler mixing ratio Number, accordingly it is also possible to which the machining property after expecting to obtain resin content ratio height, cementability, solidification or after semi-solid preparation is good Resin combination.

Moreover, resin combination filler of the invention can with disperse the resin combination filler solvent combination and Used as the paste compound containing filler, or with disperse that the resin combination uses the resin material of filler to combine and as containing The resin combination of filler uses.

Resin combination filler of the invention because have with above-mentioned composition the thermal expansion coefficient born and with pair The few effect of the adverse effect of resin.

Detailed description of the invention

Fig. 1 is the figure for indicating the crystal framework structure of the siliceous particulate material of crystallinity of the invention.

Fig. 2 is the figure for indicating the thermal expansion being measured to the resin combination of test example 2 in embodiment with filler.

Fig. 3 is the figure for indicating the thermal expansion being measured to the resin combination of test example 6 in embodiment with filler.

Fig. 4 is the figure for indicating the thermal expansion being measured to the resin combination of test example 7 in embodiment with filler.

Fig. 5 is the figure for indicating the thermal expansion being measured to the resin combination of test example 8 in embodiment with filler.

Fig. 6 is the figure for indicating the thermal expansion being measured to the resin combination of test example 13 in embodiment with filler.

Fig. 7 is swollen to the heat of the resin combination for the resin combination filler for being mixed with test example 2,8,13 in embodiment The swollen figure being measured.

Specific embodiment

Resin combination filler of the invention is for the purpose for reducing thermal expansion coefficient as far as possible, by resin combination The thermal expansion coefficient of resin combination that contains in object and can reduce.Hereinafter, based on embodiment to tree of the invention Oil/fat composition is described in detail with filler.

The resin combination filler system of present embodiment is for being dispersed in resin material and forming resin combination.Make It for combined resin material, is not particularly limited, the heat-curing resins such as epoxy resin phenolic resin can be illustrated (also comprising solid Resin before change), the thermoplastic resins such as polyester acrylate resin polyolefin.In turn, present embodiment can also be contained Filler (no matter the forms such as bulk material, threadiness) other than resin combination filler.Such as noncrystalline dioxy can also be contained The inorganic matters such as SiClx, aluminium oxide, aluminium hydroxide, boehmite, aluminium nitride, boron nitride, carbon material, by as the base for dispersing filler Organic material that resin material (material of fibrous material, particle shape) other than the resin material of matter is constituted (do not need with Resin material as matrix is strictly distinguished, it is also difficult to be distinguished).Even if resin material, other fillers have positive thermal expansion system Number has negative thermal expansion coefficient with filler by the resin combination of present embodiment, can also reduce manufactured resin The thermal expansion coefficient of composition.

It as the ratio of the resin combination filler containing present embodiment, is not particularly limited, but by increasing, energy Enough reduce the thermal expansion coefficient of finally obtained resin combination.It, can be with for example, on the basis of the quality of resin combination entirety For 5~85% or so content.

As making the resin combination of present embodiment be dispersed in filler the method in resin material, do not limit especially It is fixed, resin combination can be mixed in the dry state with filler, or some solvents as decentralized medium and can be divided It is dispersed in wherein, is mixed in resin material after forming slurry.

The resin combination of present embodiment filler system has the siliceous particulate material of crystallinity and to the crystallization The surface treating agent that the siliceous particulate material of property is surface-treated.The siliceous particulate material of crystallinity have by The crystal structure that FAU type, FER type, LTA type, MFI type and/or MWW type are constituted.Crystallinity dioxy with these crystal structures SiClx matter particulate material has negative thermal expansion coefficient.Particularly preferably FAU type.It should be noted that crystallinity silica plasmid Sub- material does not need all with these crystal structures, on the basis of all quality, if 50% or more (preferably 80% with On) there are these crystal structures.Here, the crystal framework structure of the type indicated by three letters is shown in Fig. 1.

Size distribution, the shape of particle of the siliceous particulate material of crystallinity are to contain sometimes can in resin combination Show the degree of necessary property.For example, when obtained resin combination is used for semiconductor-encapsulating material, preferably without tool There is the particulate material of the partial size bigger than the gap for invading the semiconductor-encapsulating material.Specifically, it is preferable that being 0.5 μm~50 μm or so, preferably it is substantially free of 100 μm or more of oversize grain.In addition, resin combination is used for such as printing distributing board When, preferably without the particulate material with the partial size bigger than the thickness of the insulating layer.Specifically, it is preferable that being 0.2 μm~5 μm Left and right, is preferably substantially free of 10 μm or more of oversize grain.In addition, shape of particle is preferably the low shape of length-width ratio, it is more excellent It is selected as spherical.

The siliceous particulate material of crystallinity can be by that will have the crystallinity silica of corresponding crystal structure Plasmid the operation such as is crushed alone or in combination, is classified, is granulated, being mixed as raw material and being manufactured.Using suitable in each operation When condition, number appropriate is carried out, so as to obtain the particulate material of necessary size distribution, shape of particle.For making For the crystallinity silica material of raw material itself, (such as hydrothermal synthesis method) can synthesize by conventional method.

The content of the aluminium element of the siliceous particulate material of crystallinity, on the basis of all quality, preferably 12% Hereinafter, further preferably 8% or less, 4% or less.It should be explained that, thus it is speculated that in the siliceous particulate material of preferred crystallinity Contained aluminium is close to 0%, but status is inevitably to contain mostly.

Surface treating agent is made of organo-silicon compound.By the surface treating agent that is made of organo-silicon compound on surface Reaction or attachment, can prevent the active site for promoting xanthochromia from contacting with resin.Particularly preferably silane compound, in turn, silane It, can be secured with the surface of the siliceous particulate material of crystallinity by using silane coupling agent, silazane class in compound Ground combines.It is in addition to it can cover the active site of xanthochromia of the siliceous particulate material of crystallinity as silane compound Improve with the compatibility between mixed resin material, can be using having the functional group high to the compatibility of resin material Silane compound.

As silane compound, preferably there is phenyl, vinyl, epoxy group, methacrylic acid group, amido, urea groups, mercapto Base, isocyanate group, acrylic, alkyl compound.In silane compound, as silazane class, 1,1,1,3 can be illustrated, 3,3- hexamethyldisilazane.

As the condition handled using surface treating agent the siliceous particulate material of crystallinity, do not limit especially It is fixed.For example, it is assumed that the siliceous particulate material of crystallinity is ideal sphere, using the surface area that is calculated by average grain diameter as base Standard, the area being coated by the surface treating agent (value calculated by the molecular size and treating capacity of surface treating agent.Assuming that surface treatment Agent is adhered to or is reacted with one layer on the surface of the siliceous particulate material of crystallinity) it can be for 50% or more (further It is 60% or more, 80% or more).As other benchmark, can for the table that is present in the siliceous particulate material of crystallinity The corresponding amount of the amount of the aluminium element in face is (for example, can be excessive relative to the aluminium element for being present in surface, or to confirm suppression The amount for the degree that manufacture-yellow becomes).In turn, the upper limit as the amount of surface treating agent the more more be able to suppress bad shadow to resin It rings, but if too much, then being possible to become with filler as the resin combination of present embodiment do not show negative thermal expansion system Number, therefore, the upper limit of the amount as surface treating agent, the resin combination for being set as present embodiment show that negative heat is swollen with filler The range of swollen coefficient.

The surface treatment carried out to the siliceous particulate material of crystallinity can carry out in any way.It can directly connect Touching surface treating agent makes dissolution surface treating agent solution made of some solvents be contacted and keep surface treating agent attached In the surface of the siliceous particulate material of crystallinity.The surface treating agent of attachment can also carry out heating etc. and promoting anti- It answers.